$É5 り s ^ { ~ Ä ¼ Ü ¨ Ú ä a![(ê ![(ê) : l º...¨ Û Ü é b o ¢ (ê é "8 a : * [ J Y t Y5 さ Z 5 ~ (Eqs. 1, 2) 2b, c) 2 H2PtCl6 / i-PrOH H2SiCl2 SiHCl2 + (1) neat, 55

$Page 1: $É5 り s ^ { ~ Ä ¼ Ü ¨ Ú ä a![(ê ![(ê) : l º...¨ Û Ü é b o ¢ (ê é "8 a : * [ J Y t Y5 さ Z 5 ~ (Eqs. 1, 2) 2b, c) 2 H2PtCl6 / i-PrOH H2SiCl2 SiHCl2 + (1) neat, 55$
㈻

り

㈻

り

┘

1

り

11

14

26

41

り

43

48

53

59

61

1

さ 2┊

㈻

1) 2 [PtCl3(H2C=CH2)]– d-

cis-[PtCl2(NH3)2] み 2 DNA

りよ

りり

り

㈻㈻り

◢

0, +2, +4り

Ⅴ 1769 Υ Ⅴ

100 ㈻りさ ┊

ふⅤ

りぜ

り Lewis-Lewis

10 0

さ d 9, 10 4, 56

りり

さり

オり

りり

り

り

さ (Eqs. 1, 2) 2b, c)

2

H2PtCl6 / i-PrOH

H2SiCl2

SiHCl2

(1)+neat, 55 °C

82%

SiCl3SiCl3

+ (2)H2PtCl6 / i-PrOH

neat, reflux72% 20%

HSiCl3+

り

り H2PtCl6: Speier り 3) Karstedt り [Pt2{(H2C=CHSiMe2)2O}3] 0 4 )

┞ 4b, c, d) り

セ 1 ppm り

Ⅴ ┊ りさ

DMSO ┞

, -り 5 )

り Chalk-Harrod (Scheme 1) 6) 4 2

り

PtII/Pt0

Pt(PH3)2

ゝ

よ 7) Chalk-Harrod8)

3

Scheme 1

Pt

Cl

Cl

Cl Cl

ClCl

PtCl

Cl Cl

Cl

PtCl

Cl

Cl

R'

Pt

H

Cl

Cl

SiR3Cl

R'

Pt

Cl

Cl

Cl

SiR3Cl

H

R'

R'SiR3

R'

HSiR3

R'

2–

2–

(HSiR3)

2–

Cl

Cl

+ Cl

i-PrOH IIIV

II

IVIV

–

–

–

–

–

り

り 9) り

( )

り10a)

りり11 ) り 12)

り 13, 14)

りりさ

さ (Eqs. 3, 4) 13b, 13c) り

り

り

(Eq. 5) 14d)

14e)

4

SiMe2

SiMe2

E E

(E = CO2Me)

SiMe2

Me2Si E

E

Si

Si

E

E

E

E

Me2

Me2

+ (3)

PdCl2(PPh3)4PdCl2(PhCN)2

Pt(H2C=CH2)(PPh3)2

68%

30%

71%

18%

47%

-

SiMe2X

SiMe2X

SiMe2X

SiMe2X

+Pt(PPh3)4

(4)

O

B

O O

B

O

Bu

Bu H

B BO

O O

O

Bu H

B PhO

O

Bu

Ph

H

Bu

+Pt(PPh3)4

Pd(PPh3)4

PhX Bu Br

Pd(PPh3)4 / Base

(5)

(r.t.)

(r.t.)

(reflux)

benzene

benzene, 150 °C(5 atm)

DMF, 80 °C

2Lewis り

Diels–AlderLuo 2

(Eq. 6) 15c)

∞

Diels–Alderば LUMO

(Eq. 7) 15d)

H

O

O

Ph

(BIPHEP)Pt[(S)-BINOL]

AgOTf

O O

H Ph

PtPh2P PPh2

!

OH

O

Ph+

2+

(6)CH2Cl2, r.t.

73%, 94%ee

+

O

N O

O

O

N O

O

Ph2PPt

PPh2H

O NO

O

2+

(7)

CH2Cl2, –78 °C

[(R)-BINAP]Pt(SbF6)2

99%yield

endo/exo = 97:3, 98%ee

Lewis -Lewis

5

16) Trostり 1,6- (Eq. 8)

17) (Ph3P)2Pt(OAc)2 り

さ (Eq. 9) 17d) り 1,6-ぜ (Eq. 10) 18)

-Lewis 2 18-23)

(Eq. 11) 19)

(Eq. 12) 20)

(Eq.13) 21)

Pd (8)

–

E = CO2R

E

E

E

E

Pd

E E

E EPd

E E

E E

MeO2C O PhMeO2C

O Ph(Ph3P)2Pt(OAc)2

1.3 eq. CF3CO2H

2.1 eq. DMAD

(9)

XX

PtCl2

X X

Cl2Pt

cat. PtCl2(10)

X

SiMe3

cat. PtCl2

X

PtCl2SiMe3

X

(11)

X

R1

X

PtCl2

R1

X

R1

OR2

cat. PtCl2(12)

R2OH

X

X

cat. PtCl2

X

R1

Cl2Pt

X

Cl2Pt

X

R1X

X

R1(13)

X

6

り Wackerり 2 -Lewis

り24)

り - り 25)

㌹㈻

り

(Eq. 14) 26) り

り (Eq. 15) 27) り

り (Eq. 16) 28)

OO

OO

OO5 mol% PdCl2(MeCN)22.5 eq. CuCl2

1 mol% [PtCl2(H2C=CH2)]22 mol% EuCl3

(14)

!-H Elimination

Protonation

NMe

NMe

[PtCl2(H2C=CH2)]2(15)

NMe

PtCl2

NMe

NMe

Pd(OAc)2

pyridine ligand / O2

(16)

NMe

PdLn

り

- 2 (Eqs. 17, 18) 29)

りり

-

り

7

OH

SiR ( )n

cat. L

n = 1, 2

Si = SiMe2R

OH

SiR ( )n

L protontransfer OL

SiR ( )n

– L O

RSi

( )n

(17)

NHP

SiR ( )n

cat. L

n = 1, 2

Si = SiMe2R

NHP

SiR ( )n

L protontransfer NPL

SiR ( )n

PN

RSi

( )n

(18)– L

り Lewis-Lewis

り

(Eq. 19) 30)

Prins り

Prins Lewis

OH

SiMe3

( )n

cat. PtCl2-2AgX

(X= OTf, SbF6)

n = 1, 2

Si = SiMe2R

(19)

OH

SiMe3

( )n

OR1R1CHO ( )n

㈻

(Scheme 2) 31)

(R´ � � = H) (R´ � = (CH2)4C(Me)=CH2)

Scheme 2

OH

O

R OR'

O

R OR'O R

O R

Isomerization

cyclization

! R'OH

! Hcat. PtX2

RCHO

cat. PtX2-2AgOTf

RCHO

R' = H or (CH2)4C(CH3)=CH2

X = OTf, SbF6

H

8

Lewis -Lewis 2 り

┘ り

(Scheme 3)

Scheme 3

R SiMe3

R1

OSiMe3

R1

OMe

R1

OMe

R

Ph

Ph

R

cat. PtCl2-2LiI

cat. PtCl2-2AgX

(X = OTf, SbF6)

R

PtX

R SiMe3

R1CHO

R1CH(OMe)2

R1CH(OMe)2

Ph2CHOR2

R

R

2 り

り Eq. 19┘

り

り

❻ (Eq. 20)

ふⅤ

R SiMeOH+

cat. Pt

RPt

ROMe (20)

16%

9

1) (a) Peloso, A. Coord. Chem. Rev. 1973, 10, 123. (b) Basolo, F.; Chatt, J.; Gray, H. B.; Pearson, R. G.;

Shaw, B. L. J. Chem. Soc. 1961, 2207. (c) Belluco, U.; Cattatini, L.; Basolo, F.; Pearson, R. G.; Turco, A. J. Am. Chem. Soc. 1965, 87, 241.

2) (a) Brook, M. A. Silicon in Organic, Organomtallic, and Polymer Chemistry; Wiley: New York, 2000; pp 381-458. (b) Benkeser, R. A.; Mozdzen, E. C.; Roche, R. T.; Siklosi, M. P. J. Org. Chem. 1979, 44, 1370. (c) Benkeser, R. A.; Cunico, R.; Dunny, S.; Jones, P. R.; Nerlekar, P. G. J. Org. Chem. 1967, 32, 2634.

3) (a) Speier, J. L. Adv. Organomet. Chem. 1979, 17, 407. (b) Speier, J. L.; Webster, J. A.; Barnes, G. H. J. Am. Chem. Soc. 1957, 79, 974.

4) (a) Hitchcock, P. B.; Lappert, M. F.; Warhurst, N.-J. W. Angew. Chem., Int. Ed. Engl. 1991, 30, 438. (b) Brook, M. A.; Ketelson, H. A. M.; LaRonde, F.; Pelton, R. H. Inorg. Chim. Acta 1997, 264, 125. (c) Brook, M. A.; Ketelson, H. A. M.; Pelton, R. H.; Heng, Y. M. Chem. Mater. 1996, 8, 2195. (d) Hu, C.-Y.; Han, X.-M.; Jiang, Y.-Y.; Liu, J.-G; Shi, T.-Y. J. Macromol. Sci., Chem. 1989, A26, 349.

5) (a) Lewis, L. N.; Sumpter, C. A.; Davis, M. J. Inorg. Organomet. Polym. 1995, 5, 377. (b) Lewis, L. N.; Sumpter, C. A.; Stein, J. J. Inorg. Organomet. Polym. 1996, 6, 123. (c) Lewis, L. N.; Stein, J.; Colborn, R. E.; Gao, Y.; Dong, J. J. Organomet. Chem. 1996, 521, 221.

6) Chalk, A. J.; Harrod, J. F.; J. Am. Chem. Soc. 1965, 87, 16. 7) Sakaki, S.; Ieki, M. J. Am. Chem. Soc. 1993, 115, 2373. 8) (a) Lewis, L. N.; Lewis, N. J. Am. Chem. Soc. 1986, 108, 7228. (b) Lewis, L. N.; Uriarte, R. J.; Lewis, N.

J. Catalysis 1991, 127, 67. (c) Faglioni, F.; Blanco, M.; Goddard, W. A. III.; Saunders, D. J. Phys. Chem. B 2002, 106, 1714.

9) (a) Marciniec, B. Silicon Chemistry 2002, 1, 155. (b) Kuhnen, T.; Stradiotto, M.; Ruffolo, R.; Ulbrich, D.; McGlinchey, M. J.; Brook, M. A. Organometallics 1997, 16, 5042. (c) Lewis, L. N.; Uriarte, R. J. Organometallics 1990, 9, 621.

10) (a) Guliński, J.; James, B. R. J. Mol. Catal. 1992, 72, 167. (b) Sakaki, S.; Mizoe, N.; Sugimoto, M. Organometallics 1998, 17, 2510.

11) (a) Onopchenko, A.; Sabourin, E. T.; Beach, D. L. J. Org. Chem. 1983, 48, 5101. (b) Onopchenko, A.; Sabourin, E. T.; Beach, D. L. J. Org. Chem. 1984, 49, 3389. (c) Ojima, I.; Fuchikami, T.; Yatabe, M. J. J. Organomet. Chem. 1984, 260, 355. (d) Süss-Fink, G.; Reiner, J. J. Mol. Catal. 1982, 16, 231. (e) Seki, T.; Takeshita, K.; Kawamoto, K.; Murai, S.; Sonoda, N. Angew. Chem., Int. Ed. Engl. 1980, 19, 928. (f) Christ, M. L.; Sabo-Etienne, S.; Chaudret, B. Organometallics 1995, 14, 323.

12) Svododa, P.; Sedlmayer, P.; Hetflejs, J.; Coll. Czech. Chem.Commun. 1973, 38, 1783. 13) (a) Suginome, M.; Ito, Y. Chem. Rev. 2000, 100, 3221. (b) Kusukawa, T.; Kabe, Y.; Nestler, B.; Ando, W.

Organometallics 1995, 14, 2556. (c) Hayashi, T.; Kobayashi, T.-a.; Kawamoto, A. M.; Yamashita, H.: Tanaka, M. Organometallics 1982, 9, 280. (d) Watanabe, H.; Kobayashi, M.; Higuchi, K.; Nagai, Y. J. Organomet. Chem. 1980, 186, 51.

14) (a) Beletskaya, I.; Moberg, C. Chem. Rev. 1999, 99, 3435. (b) Ishiyama, T.; Matsuda, N.; Miyaura, N.; Suzuki, A. J. Am. Chem. Soc. 1993, 115, 11018. (c) Ishiyama, T.; Matsuda, N.; Murata, M.; Ozawa, F.; Suzuki, A.; Miyaura, N. Organometallics 1996, 15, 713. (d) Ishiyama, T.; Yamamoto, M.; Miyaura, N. Chem. Lett. 1996, 1117. (e) Cui, Q.; Musaev, D. G.; Morokuma, K. Organometallics 1997, 16, 1355. (f) Lesley, G.; Nguyen, P.; Taylor, N. J.; Marder, T. B.; Scott, A. J.; Clegg, W.; Norman, N. C. Organometallics 1996, 15, 5137. (g) Iverson, C. N.; Smith, M. R. III Organometallics 1996, 15, 5155.

15) (a) Kündig, E. P.; Saudan, C. M. In Lewis Acids in Organic Synthesis, Vol. 2; Yamamoyo, H., Ed.;

10

Wiley-VCH: Weinheim, 2000, 597. (b) Fujimura, O. J. Am. Chem. Soc. 1998, 120, 10032. (c) Luo, H.-K.; Schumann, H. J. Mol. Catal. A. 2006, 248, 42. (d) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999, 1, 2157. (e) Brunkan, N. M.; White, P. S.; Gagné, M. R. Organometallics 2002, 21, 1565. (f) Brunkan, N. M.; White, P. S.; Gagné, M. R. Organometallics 2002, 21, 1576. (g) Oi, S.; Terada, E.; Ohuchi, K.; Inoue, Y. J. Org. Chem. 1999, 64, 8660. (h) Nishibayashi, Y.; Yoshikawa, M.; Inada, Y. Milton, M. D.; Hidai, M.; Uemura, S. Angew. Chem. Int. Ed. 2003, 42, 2681.

16) (a) Chisholm, M. H.; Clark, H. C. Acc. Chem. Res. 1973, 6, 2681. (b) Belluco, U.; Bertani, R.; Michelin, R. A.; Mozzon, M. J. Organomet. Chem. 2000, 600, 37.

17) (a) Trost, B. M.; Tanoury, G. J. J. Am. Chem. Soc. 1988, 110, 1638. (b) Trost, B. M.; Trost, M. K.. J. Am. Chem. Soc. 1991, 113, 1850. (c) Trost, B. M.; Yanai, M.; Hoogsteen, K. J. Am. Chem. Soc. 1993, 115, 5294. (d) Trost, B. M.; Chang, V. K. Synthesis 1993, 824.

18) (a) Chatani, N.; Morimoto, T.; Muto, T.; Murai, S. J. Am. Chem. Soc. 1994, 116, 6049. (b) Chatani, N.; Furukawa, N.; Sakurai, H.; Murai, S. Organometallics 1996, 15, 901.

19) Fernández-Rivas, C.; Méndez, M.; Echavarren, A. M. J. Am. Chem. Soc. 2000, 122, 1221. 20) Méndez, M.; Muñoz, M. P.; Echavarren, A. M. J. Am. Chem. Soc. 2000, 122, 11549. 21) (a) Chatani, N.; Kataoka, K.; Murai, S.; Furukawa, N.; Seki, Y. J. Am. Chem. Soc. 1998, 120, 9104. (b)

Chatani, N.; Inoue, H.; Ikeda, T.; Murai, S. J. Org. Chem. 2000, 65, 4913. 22) (a) Fürstner, A.; Szillat, H.; Gabor, B.; Mynott, R. J. Am. Chem. Soc. 1998, 120, 8305. (b) Fürstner, A.;

Stelzer, F.; Szillat, H. .; Méndez, M.; Echavarren, A J. Am. Chem. Soc. 2001, 123, 11863. (c) Fürstner, A.; Davies, P. W.; Gress, T. J. Am. Chem. Soc. 2005, 127, 8224.

23) Oi, S; Tsukamoto, I.; Miyano, S.; Inoue, Y. Organometallics 2001, 20, 3704. 24) (a) Chianese, A. R.; Lee, S. J.; Gagné, M. R. Angew. Chem. Int. Ed. 2007, 46, 4042. (b) Haan, C. Chem.

Eur. J. 2004, 10, 5888. 25) Lersch, M.; Tilset, M. Chem. Rev. 2005, 105, 2471. 26) (a) Widenhoefer, R. A. Pure. Appl. Chem. 2004, 76, 671. (b) Widenhoefer, R. A.; Liu, C. Tetrahedron.

Lett. 2005, 46, 285. (c) Yang, D.; Li, J.-H.; Gao, Q.; Yan, Y.-L. Org. Lett. 2003, 5, 2869. 27) Liu, C.; Han, X.; Wan, X.; Widenhoefer, R. A. J. Am. Chem. Soc. 2004, 126, 3700. 28) Ferreira, E. M.; Stoltz, B. M. J. Am. Chem. Soc. 2003, 125, 9578. 29) (a) Miura, K.; Okajima, S.; Hondo, T.; Hosomi, A. Tetrahedron. Lett. 1995, 36, 1483. (b) Miura, K.;

Hondo, T.; Okajima, S.; Hosomi, A. Tetrahedron. Lett. 1996, 37, 487. (c) Miura, K.; Okajima, S.; Hondo, T.; Nakagawa, T.; Takahashi, T.; Hosomi, A. J. Am. Chem. Soc. 2000, 122, 11348. (d) Miura, K.; Hondo, T.; Nakagawa, T.; Takahashi, T.; Hosomi, A. Org. Lett. 2000, 2, 385. (e) Miura, K.; Takahashi, T.; Nishikori, H,; Hosomi, A. Chem. Lett. 2001, 958.

30) Miura, K.; Itaya, R.; Horiike, M.; Izumi, H.; Hosomi, A. Synlett. 2005, 3148. 31) Miura, K.; Horiike, M.; Inoue, G.; Ichikawa, J.; Hosomi, A. Chem. Lett. in press.

11

り

さ

1990 5よ

さ㌹ (Eq. 1)

┘ (Eq. 2) 1)

NaOH NaCl+ + (1)

O

Cl OH

cat. Li3PO4OH (2)

ぜ

(Riley ) 1,3-Prins -Baylis-Hillman

りり

(Eq. 3) 2) ┘ palytoxin (Figure 1) 3)

↓4)

Figure 1.

O

H2N OH

O

O

OH

OH

O

HO OH

OH OH

OH OH

Me

OH

HO

HO

OH

O

OH

OH

OH

O

HO

OH

HO

OH

OH

OH

Me

OOH

OHOH

OH

OH

HOHO

OO

Me

MeMe OH

HOOH

OH

OOH

OH

OHHO

NH

MeO HOOH

OH

Me

OH

O

NH

HO

palytoxin

12

R1X

cat. NiCl22 eq. CrCl2

R1NiX

R1CrX2

CrX3

- NiX2 R1 OH

R2 R3R2

O

R3

(3)

0 り

Montgomery (Eq. 4) 5) Jamison3 (Eq.

5) 6) モさ

Ⅴ

R1 H +R2

O

H

O

LNi

R1

H R2phosphine ligand

cat. Ni(cod)2 R32Zn OH

R2R1(4)

R3

R1

R2

O

H

R3SiOTfcat. Ni(cod)2

phosphine ligand

O

LNi

R1 R2

OSiR3

R2

R1

+ + (5)R3SiOTf

Et3N

ふⅤ り

-, - (Eq. 6) 7)

- り

(Eq. 7) 8)

R2

R1

SiMe3

R3EX-AlCl3

" E "

R2R1

ER3

R2

R1

E

R3SiMe3

(6)

EX = RCCl, ROCH2Cl, etc.

O

C !-Silylcarbenium Ion

R2

R1

SiYMe2

R3ArX-cat.Pd(0)

" Ar-Pd-X "

F R2

R1

PdAr

R3

R2

R1

Ar

R3

Y = OR, F, etc. Vinylpalladium

(7)

(Eq. 8) 9) り

(cine ) (Eq. 9) 10)

13

OX OO

SiMe3 SiMe3

Lewis Acid+

traceX = MEM, MOM, CH2Cl

(8)

H

Ar1

SiMe3

H

Ar2N2BF4+cat. Pd(OAc)2

H

Ar1

Ar2

H

Ar2

Ar1

H

H

+ (9)

22 り

(Eq. 10) 11)

Prins

┘

(Scheme 1)

OH

SiMe3

( )n

cat. PtCl2-2AgX

(X= OTf, SbF6)

n = 1, 2

Si = SiMe2R

(10)

OH

SiMe3

( )n

OR1R1CHO ( )n

Scheme 1

R SiMe3cat. Pt (II)

R SiMe3

? Ph

OSiMe3

Ph

OSiMe3

R

R

PhCHO

PhCHO

14

1a

2 (Z)- 1a 1,2- (DCE) り

(10 mol%) 2a 13% (Entry 1 in Table 1)

(THF) 1,2- (DME) (Entries 2–4)

(CuCl2, NiCl2, PdCl2, RhCl3, IrCl3, AuCl3, [RhCl(cod)]2 ) り

┘

0 り (Entries 6 and 7) DCE 々

(Entry 8) (Entries 9–12) り

々

┘ (Entry 13) DCE り

(Entry 16) DME り

(Entry 17) (Entries 18 and 19)

り (Entries 20–25)

2a (Entry 25)

(Entries 12 and 26) り ┘

1a

(Table 2) ┘

2 (Entries 3, 4, 7–11) 4- 4-

(Entries 5 and 6) 2 (Entries 7–11) 2-

4-

2 々 2 (Entries 12–15) 4-

24 2 (Entry 16) ├

2 (Entry 17)

15

2 (Entries 18 and 19) (Entry 20) , -

(Entries 21 and 22)

Table 1. Optimization of Reaction Conditions

n-C10H21 SiMe3Ph

O

HPh

OSiMe3

n-C10H21

Catalyst (10 mol%)

Additive (20 mol%)

70 °C, 24 h

+ + Ph

OH

n-C10H211a (2 eq.)

2a alcohol Yield / %

Entry Catalyst Additive Solvent 2a alcohol

1 PtCl2 - (CH2Cl)2 13 1

2 PtCl2 - THF 10 7

3 PtCl2 - diglyme 15 3

4 PtCl2 - (CH2OMe)2 24 <3

5 PtCl2 - AcOEt 16 <1

6 Pt(PPh3)4 - (CH2Cl)2 0 0

7 Pt(dba)2 - (CH2Cl)2 0 0

8 PtCl4 - (CH2Cl)2 <37 <4

9 PtCl2(COD) - (CH2Cl)2 0 0

10 cis-PtCl2(PPh3)2 - (CH2Cl)2 0 0

11 (2,2-bipyridine)PtCl2 - (CH2Cl)2 1 0

12 cis-PtCl2(PhCN)2 - (CH2Cl)2 10 0

13 PtCl2 AgOTf (CH2Cl)2 0 0

14 PtBr2 - (CH2Cl)2 <12 trace

15 PtBr2 - (CH2OMe)2 trace trace

16 PtI2 - (CH2Cl)2 70 <1

17 PtI2 - (CH2OMe)2 0 0

18 PtI4 - (CH2Cl)2 46 4

19 PtI4 - (CH2OMe)2 24 <10

20 PtCl2 AgI (CH2Cl)2 4 0

21 a PtCl2 KI (CH2Cl)2 28 0

22 PtCl2 KI (CH2Cl)2 77 <10

23 a PtCl2 NaI (CH2Cl)2 39 0

24 PtCl2 NaI (CH2Cl)2 65 3

25a PtCl2 LiI (CH2Cl)2 82 0

26b cis-PtCl2(PhCN)2 LiI (CH2Cl)2 26 trace aThe reaction time is 2 h. bThe reaction time is 12 h.

16

Table 2. Pt-Catalyzed Reaction with Various Aldehydes

n-C10H21 SiMe3R

O

HR

OSiMe3

n-C10H21

PtCl2 (10 mol%)

LiI (20 mol%)

(CH2Cl)270 °C

+

1a (2 eq.)2

Entry R Time / h Product Yield / %

1 Ph 2 2a 82

2 1-Naphthyl 24 2b 84

3 4-O2N-C6H4 24 2c 84

4 4-MeO2C-C6H4 48 2d 77

5 4-NC-C6H4 48 2e 45

6 4-Ac-C6H4 48 2f 28

7 4-F-C6H4 24 2g 89

8 4-Cl-C6H4 5 2h 90

9 2-Cl-C6H4 48 2i 86

10 4-Br-C6H4 48 2j 91

11 4-I-C6H4 36 2k 71

12 4-Me-C6H4 5 2l 58

13 4-Me-C6H4 24 2l <19

14 4-MeO-C6H4 2 2m 18

15 4-MeO-C6H4 24 2m 0

16 4-AcO-C6H4 24 2n 69

17 n-C6H13 5 - 0

18 Et2CH 2 2o 13

19 c-C6H 11 5 2p 38

20 t-Bu 24 - 0

21 PhCH=CH 2 - 0

22 H2C=CHMe 24 2q 7

1a 4-

1a 4- (Entries 1 and 2 in Table 3)

2

(Entries 3 and 4) 4 Ⅴ

2 24 々

2┘ 2 24

(Entry 5) THF 々

(Entry 6) (Entry 7)

17

(Entry 9) DMF ┘

(Entries 10 and 11)

Table 3. Reaction of 4-Methoxybenzaldehyde

n-C10H21 SiR3

O

H

OSiR3

n-C10H21

Catalyst (10 mol%)

Additive

70 °C

+

1 (2 eq.)2

MeO MeO

Entry Catalyst Additive R Solvent Time / h Yield / %

1 PtCl2 LiI (20 mol%) Me (CH2Cl)2 2 18

2 PtCl2 LiI (20 mol%) Me (CH2Cl)2 24 0

3 PtCl2 LiI (20 mol%) Et (CH2Cl)2 4 13

4 PtCl2 LiI (20 mol%) Et (CH2Cl)2 24 0

5 PtCl2 – Me (CH2Cl)2 24 5

6 PtCl2 – Me THF 24 <40

7 PtCl2 LiI (20 mol%) Me THF 24 0

8 PtI2 – Me THF 24 <18

9 PtCl2 K2CO3 (1.0 eq.) Me THF 24 9

10 PtCl2 – Me MeCN 24 0

12 PtCl2 – Me DMF 24 0

4 24 (Eq. 11) り 2m

42a 4-

n-C10H21 SiMe3Ph

O

H

Ph

OSiMe3

n-C10H21

PtCl2 (10 mol%)

LiI (20 mol%)

(CH2Cl)2

70 °C, 24 h

+

1a (2 eq.)

2a, 2%

+

O

H

MeO

Ph

O

H

+

O

H

MeO

+

OSiMe3

n-C10H21

+

MeO2m, 0%92% 71%

(11)(1 eq.) (1 eq.)

GC Yield

1a

(Eq. 12)

(Table 4)

18

OSiMe3

H

Me3SiI

– HI

O

H (12)

┘ 2p (Entries 1 and 2) ┘

2p (Entries 3 and 4)

┘ (Entries 5, 6) ┘

Lewis さ

2p (Entry 12) Lewis

(Entries 17 and 18) (Entry 19)

Table 4. Pt-Catalyzed Reaction with Cyclohexanecarbaldehyde

n-C10H21 SiMe3

O

H

OSiMe3

n-C10H21

PtCl2 (10 mol%)

MIn

(CH2Cl)2

70 °C, 4 h

+

1a (2 eq.)2p

Entry MIn mol% Yield / % Entry MIn mol% Yield / %

1a LiI 20 38 11 TiI4 10 0

2 LiI 10 57 12 MnI2 10 71

3 LiI 5 31 13 FeI2 10 56

4 - - 2 14 NiI2 10 7

5 NaI 20 63 15 a ZnI2 10 0

6 NaI 10 69 16 InI3 10 0

7 KI 20 14 17 CeI3 10 43

8 CsI 10 6 18 SmI3 10 14

9 a MgI2 10 48 19 b , c PtI2 10 67

10 CaI2 10 27 aThe reaction time is 5 h. bThe reaction time is 24 h. cWithout PtCl2.

2-

19

n-C10H21 SiMe3

O

H

OSiMe3

n-C10H21

PtCl2 (10 mol%)

MIn (10 mol%)

(CH2Cl)2, 70 °C+

1a (2 eq.)2o

13%

14%

30%

LiI*

NaI

MnI2

(2 h)

(4 h)

(2 h)

(13)

*20 mol%

(Table 5) 1a ((E)-1a) モ Z

り (Entry 2) 1b (Entry 3)

1c 1d┘ (Entries 4 and 5)

1e (Entry 6) 1d

(Entries 7 and 8) 1f 1f

々 (Entry 7) 1g

(Entry 8) t-1h 1i 1j

(Entries 9–11)

1b 4-

り ┘

(Eq. 14)

Me SiMe3

PtCl2 (5 mol%)

LiI (10 mol%)

(CH2Cl)2

70 °C, 24 h1b (2 eq.)

+

O

H

Cl

OSiMe3

MeCl

2r', 91%

(14)

20

Table 5. Pt-Catalyzed Reaction of Various Vinylsilanes with Benzaldehyde

R SiPh

O

HPh

OSi

R

PtCl2 (10 mol%)

LiI (20 mol%)

(CH2Cl)270 °C

+

1 (2 eq.)2

Entry Vinylsilane R Si Time / h Product Yield / %

1 1a n-C10H21 SiMe3 2 2a 82

2 (E)-1a n-C10H21 SiMe3 24 2a 60

3 1b Me SiMe3 2 2r 78

4 1c H SiMe3 2 - 0

5 1d c-C6H 11 SiMe3 24 2s 5

6 1e Ph SiMe3 10 2t 69

7 1f 4-MeO-C6H4 SiMe3 2 - C.M.

8 1g 4-CF3-C6H4 SiMe3 24 2v 6

9 1h n-C10H21 SiMe2tBu 24 2w 29

10 1i n-C10H21 SiMe2Ph 10 2x 60

11 1j n-C10H21 SiEt3 10 2y 82

1a

4 (Eqs. 15 and 16) 4-2h

3b 4b1a

R

OMe

OMeR

OSiMe3

n-C10H21

PtCl2 (10 mol%)

LiI (20 mol%)

(CH2Cl)2, 70 °C+

1a (2 eq.)

R

OMe

n-C10H21

R

OMe

n-C9H19

+ +

2a, 0%

2h, 41%

3a, 26%

3b, 29%

4a, 3%

4b, 11%

R = Ph (2 h)

R = 4-Cl-C6H4 (24 h)

(15)n-C10H21 SiMe3

as above

24 h

+1a (2 eq.)Ph

O

n-C10H21

Ph

O

n-C9H19

+

3c, 33% 4c, 4%

O

O

Ph

OSiMe3 OSiMe3

(16)

, - 55´ (Eqs. 17 and 18) 5´ �

5´ �

21

OO

n-C10H21

O n-C10H21+

1a (2 eq.)

PtCl2 (10 mol%)

LiI (20 mol%)

(CH2Cl)270 °C, 24 h

+ (17)

5a, 15% 5a', 10%

n-C10H21 SiMe3

+1a (2 eq.)

PtCl2 (10 mol%)

LiI (20 mol%)

(CH2Cl)2

70 °C, 24 h

+ (18)

5b, 2% 5b', 1%

OO

n-C10H21

O

n-C10H21

Scheme 26

67 1,2-

2 Lewis

Scheme 2. A Possible Mechanism

R1 Si R2

SiO PtX2

R1 H

R2

SiO PtX2

R1 H

R'2

SiO PtX2

R1

H

R2

SiO

R1

PtX2 R'CHO

R1PtX

– PtX2Si = SiR3

X = Cl, I

SiX+

61

7

7'

2

Noels り

ぜ (Eqs. 19 and 20) 12)

り 1aよ ❻ 8 (Eq.

21) (Eq. 22) 8

6 13) 9 (Scheme 3) 8 Scheme 2

22

ROH N2CHCO2Et

H

LnPt

CO2Et

H

LnPt

CO2Et

RO-CH2CO2Et+ROH

OH N2CHCO2Et OCH2CO2Et

OO

HCO2Et

HHOH2C

+ + +cat. Pt

(19)

(20)cat. Pt

n-C10H21 SiMe3n-C10H21

OMePtCl2 (5 mol%), LiI (10 mol%)

MeOH-(CH2Cl)2 (1:1)

70 °C, 24 h 8. 16%1a

(21)

n-C10H21

OMeas above

MeOD-(CH2Cl)2 (1:1)

8-D. 15%

1a

(85%D) D

D (>99%D)

(22)

Scheme 3

RPtX

R = n-C10H21, Si = SiMe3, X = Cl, I

RPtX2SiX+

MeOH

– MeOSi96

1a

PtX2

– PtX2

8

MeOH

7 1,2-1a-D

モ ❻ ㎲

(Eq. 23) 1,2-

n-C10H21 SiMe3 Ph

O

HPh

OSiMe3

n-C10H21

PtCl2 (10 mol%)

LiI (20 mol%)

(CH2Cl)270 °C, 4 h

+

1a-D (2 eq., 92%D) 2a-D, 87% (86%D)

D

D (23)

Scheme 2 ッ

1b 1i り

2r 2r´ � 2x 2a 1 : 1

2r 2x (Eq. 24) 2r´ � 2a 1b 1i

1a-D 1k (Eq. 25)

23

6´ �さ (Scheme 4) 6´

Me SiMe3Ph

O

H

Ph

OSiMe3

Me

+

+ Ph

OSiMe2Ph

Me

1b (1 eq.)

2r 2r'

+ n-C10H21 SiMe2Ph

PtCl2 (10 mol%)

LiI (20 mol%)

(CH2Cl)2

70 °C, 4 h

+ Ph

OSiMe2Ph

n-C10H21

2x

+ Ph

OSiMe3

n-C10H21

2a

1i (1 eq.)

39%, 92 : 8 39%, 95 : 5

(24)

n-C10H21 SiMe2CH2DPh

O

H

Ph

OSiMe2CH2D

n-C10H21

+

+ Ph

OSiMe3

n-C10H21

1a-D' (1 eq.)

2a-D' 2a

+ n-Bu SiMe3

as above

+ Ph

OSiMe3

n-Bu

2z

+ Ph

OSiMe2CH2D

n-Bu

2z-D'

1k (1 eq.)

43%, 92 : 8 39%, 93 : 7

(25)

Scheme 4. A Revised Mechanism

R1 Si R2

SiO PtX2

R1 H

PtX2 R2CHO

R1PtX2

Si = SiR3

X = Cl, I

6'1

7PtX2

R2

OSi

R1

Si

2ッ

モり

Grignard モ々 (Eq. 26)

り

㈻ ┘

11 1a1.3- (Eq. 27) 2

り 0

24

PhBr

Mg (4.0 eq.)

THF

r.t., 30 min

ZnCl2 (2.0 eq.)

THF / Et2O

r.t., 1.5 h

PtCl2 (10 mol%)

LiI (20 mol%)

PhCHO (1.0 eq.)

(CH2Cl)2

–30 °C to r.t., 1 h

Complex mixture. Ph

OH

Ph10a (4.0 eq.)

(26)

Not Observed

Ph

O

H

PtCl2 (10 mol%)

(CH2Cl)270 °C, 24 h

+PhSnBu3

PhPh

11 (1.0 eq.)

(27)

none :

LiI (20 mol%) :

1a, LiI (20 mol%) :

trace

trace

trace

0├ 10b

┘

(Eq. 28) [(PhCH=CH-)Pt(PPh3)2I]

モ

┘ り

0 (dba) 10b 1,3- (Eq. 29) dba

PhI

Pt(PPh3)4 (1.0 eq.) PhCHO (2.0 eq.)

No reaction. Ph

OR

Ph

Not Observed

Ph

OR

Ph

Not Observed

PhPh

(28)

(29)

10b

PhMe or (CH2Cl)2r.t. ~ 100 °C

Pt(dba)2 (1.0 eq.) PhCHO (2.0 eq.)10b

ConditionLiI (2-6 eq.)

Me3SiI (2 eq.)Additive

り 12 (Scheme 5) 12

2

25

Scheme 5. Hydrosilylation

R SiH+

PtX2 Pt Si

R

H Si

R

12

Ph

OSi

R

PhCHO

2

1- り

70 Υ 2y (Eq. 30) 2y

2y13i

(Eq. 31) 14)

n-C10H21

Ph

O

H

Et3SiH Ph

OSiEt3

n-C10H21

n-C10H21

SiEt3+ +PtCl2 (10mol%)

(CH2Cl)2, 24 h(2.0 eq.) (2.0 eq.)

+ (30)

2y

5%

0%

70 °C

r.t.

(E)-1i

<72%

80%

n-C10H21

Ph

O

H

Et3SiH+ +

PtCl2 (10mol%)

LiI (20 mol%)

(CH2Cl)2

70 , 24 h(2.0 eq.) (2.0 eq.)

n-C10H21 SiEt3

13i, 52%

(31)

ッ

Scheme 415) 0 り 6)

0 り

り 22 4 り

り

ぜ

さ

26

Ⅴ

Glass Tube Oven GTO-250 RS Ⅴ (bath temp.) (IR) FT/IR-230 ゝ

(1H NMR, 13C NMR) JEOL JNM-EX270 (1H NMR, 0.00 ppm) (1H NMR (CHCl3), 7.26 ppm), (13C NMR, 77.0 ppm ( )) (1H NMR (C6HD5), 7.16 ppm; 13C NMR, 128.0 ppm (

)) ㈻ QP-5050GC-17A ( DB-1 30.0 m 0.25 µl

0.25 mmID 100 kPa 32.5 cm / sec 15 1.40 mL / min2.5 mL / min N2)

モ

(THF) (Et2O) (DME)

⇩ (CH2Cl2) (DCE) (AcOEt)

⇩

モ

❻

モ

モオ

(Z)-1- (1a): [70875-37-8]16)

n-C10H21 SiMe3 1- (10.1 g, 60.7 mmol) THF (130 mL) 0 Υ

n- (1.62 M in hexanes, 41.2 mL, 66.8 mmol) 0 Υ 2 (8.54 mL, 66.8 mmol) 0 Υ

↓ 18 (50 mL 2) ⇩

1- -1- (13a, 13.8 g, 57.9 mmol) 95% Bp 83–86 °C (0.50 Torr). 1H NMR (CDCl3) δ 0.15 (s, 9H), 0.88 (t, J = 6.4 Hz,

27

3H), 1.26–1.56 (m, 16H), 2.21 (t, J = 6.9 Hz, 2H). 13a (13.8 g, 57.9 mmol) Et2O (120 mL) 0 Υ

DIBAL-H (0.94 M in n-hexane, 68 mL, 64 mmol) ↓

36 0 Υ 20 w%2 M (50 mL

2) ⇩

(Z)-1- -1- (1a, 13.1 g, 54.5 mmol) 94%Bp 68–72 °C (0.45 Torr). 1H NMR (CDCl3) δ 0.11 (s, 9H), 0.88 (t, J = 6.9 Hz, 3H), 1.26–1.36 (m, 16H), 2.11 (q, J = 6.9 Hz, 2H), 5.46 (d, J = 14.0 Hz, 1H), 6.30 (dt, J = 14.0, 6.9 Hz, 1H); 13C NMR (CDCl3) δ 0.2 (CH3

3), 14.1 (CH3), 22.7 (CH2), 29.4 (CH2 2), 29.59 (CH2), 29.62 (CH2 2), 29.8 (CH2), 31.9 (CH2), 33.6 (CH2), 128.7 (CH), 149.4 (CH); MS m/z (relative intensity) 240 (M+, 0.63), 225 (M+ – Me, 27), 73 (100). (E)- -1- ((E)-1a): [70875-31-9]16)

n-C10H21

SiMe3

(E)-1a 1a 17) (4.0 mL) 1a (1.20 g, 5.00 mmol) Bu3SnH (146 mg) Et3B (1.01 M in n-hexane, 495 µL, 0.50 mmol) 60 Υ 24

DBU(E)- -1- ((E)-1a) 82% (E:Z = 97:3) 1H NMR

(CDCl3) δ 0.04 (s, 9H), 0.88 (t, J = 6.6 Hz, 3H), 1.26–1.41 (m, 16H), 2.09 (q, J = 6.4 Hz, 2H), 5.61 (dt, J = 18.6, 1.5 Hz, 1H), 6.02 (dt, J = 18.6, 6.4 Hz, 1H); 13C NMR (CDCl3) δ –1.1 (CH3 3), 14.1 (CH3), 22.7 (CH2), 28.7 (CH2), 29.2 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 31.9 (CH2), 36.8 (CH2), 129.5 (CH), 147.5 (CH); MS m/z (relative intensity) 240 (M+, 1.8), 225 (M+ – Me, 48), 73 (100). (Z)-1- (1b): [4964-02-7]18)

Me SiMe3 1b (Z)-1- 18) (4.0 g,

0.58 mol) Et2O (100 mL) -28 Υ (Z)-1- (10.0 g, 82.7 mmol) Et2O (50 mL) 18

0 Υ (10.6 mL, 82.7 mmol) Et2O (50 mL) 0 Υ ↓ 22

(100mL 2) ⇩

(Z)-1- (1b, 4.09 g, 91 w%) 39% 1b Bp 88–90 °C. 1H NMR (CDCl3) δ 0.12 (s, 9H), 1.78 (dd,

J = 7.0, 1.6 Hz, 3H), 5.50 (dq, J = 14.0, 1.6 Hz, 1H), 6.39 (dq, J = 14.0, 7.0 Hz, 1H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 19.0 (CH3), 130.0 (CH), 143.1 (CH); MS m/z (relative intensity) 114 (M+, 12), 99 (M+ – Me, 100), 73 (68). (Z)-2- -1- ( ) (1d): [66270-75-5]19)

28

SiMe3

1d 20)

(17.3 g, 66.0 mmol) (80 mL) (2.24 g, 20.0 mmol) 0 Υ

(10 mL) (14.6 g, 44.0 mmol) 101.5 (600 mL)

60 Υ/0.5 Torr 1,1- -2- 14, 4.69 g, 17.5 mmol88% Bp 60 °C (bath temp., 0.50 Torr). 1H NMR (CDCl3) δ 1.04–1.37 (m, 6H), 1.63–1.75 (m, 4H),

2.21–2.35 (m, 1H), 6.23 (d, J = 9.1 Hz, 1H). 13 (4.69 g, 17.5 mmol) THF (35 mL) -78 Υ

(1.67 M in hexanes, 21.3 mL, 35.0 mmol) 78 Υ 1↓ 15 (20 mL 3)

1- -2- (13d, 2.55 g, 14.1 mmol) 81% Bp 80-85 °C (8.5 Torr). 1H NMR (CDCl3) δ 0.14 (s, 9H), 1.24–1.79 (m, 10H), 2.33–2.42 (m, 1H).

13d 1d 13a 1a 1H NMR (CDCl3) δ 0.11 (s, 9H), 1.01–1.74 (m, 10H), 2.08–2.21 (m, 1H), 5.36 (d, J = 14.0 Hz, 1H), 6.11 (dd, J = 14.0, 10.0 Hz, 1H); 13C NMR (CDCl3) δ 0.4 (CH3 3), 25.8 (CH2 2), 25.9 (CH2), 33.1 (CH2 2), 42.7 (CH), 126.6 (CH), 155.0 (CH); MS m/z (relative intensity) 182 (M+, 5.6), 167 (M+ – Me, 10), 73 (100). (Z)-1- -2-( ) (1e): [19319-11-0]21)

Ph SiMe3 1e 1a 1H NMR (CDCl3) δ 0.05

(s, 9H), 5.83 (d, J = 15.2 Hz, 1H), 7.21–7.32 (m, 5H), 7.37 (d, J = 15.2 Hz, 1H); 13C NMR (CDCl3) δ 0.2 (CH3 3), 127.3 (CH), 127.9 (CH 2), 128.1 (CH 2), 132.8 (CH), 140.1 (C), 146.6 (CH); MS m/z (relative intensity) 176(M+, 27), 161 (M+ – Me, 100), 73 (15). (Z)-1- (4- )-2-( ) (1f): [119327-32-1]19)

Me3Si

MeO

1f (4- ) 1a 1H NMR

(C6D6) δ 0.16 (s, 9H), 3.27 (s, 3H), 5.80 (d, J = 15.0 Hz, 1H), 6.74 (dt, J = 8.7, 2.6 Hz, 2H), 7.24 (dt, J = 8.7, 2.6 Hz, 2H), 7.38 (d, J = 15.0 Hz, 1H); 13C NMR (C6D6) δ 0.4 (CH3 3), 54.7 (CH3), 113.7 (CH 2), 129.8 (CH 2), 130.6 (CH), 133.0 (C), 146.9 (CH), 159.7 (C); MS m/z (relative intensity) 206 (M+, 42), 191 (M+ – Me, 100). (Z)-1- (4- )-2-( ) (1g)

Me3Si

F3C

29

1g (4- ) 1a IR (neat) 1325, 1250, 1128 cm–1; 1H NMR (CDCl3) δ 0.05 (s, 9H), 5.97 (d, J = 15.3 Hz, 1H), 7.29 (d, J = 15.3 Hz, 1H), 7.37 (d, J = 8.2 Hz, 1H), 7.57 (d, J = 8.2 Hz, 1H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 124.2 (C, 1J(13C-19F) = 272.4 Hz), 124.9 (CH 2, 3J(13C-19F) = 3.4 Hz), 128.3 (CH), 129.3 (C, 2J(13C-19F) = 32.5 Hz), 135.5 (CH), 143.7 (C), 144.9 (CH); MS m/z (relative intensity) 244 (M+, 16), 229 (M+ – Me, 100), 73 (27). Anal. Calcd for C12H15F3Si: C, 58.99; H, 6.19. Found: C, 58.72; H, 6.27. (Z)- 1-tert- -1- (1h): [183290-32-6]22)

n-C10H21 SiMe2tBu

1h 1a 1H NMR (CDCl3) δ 0.08 (s, 6H), 0.88 (br s, 12H), 1.25–1.40 (m, 16H), 2.10 (q, J = 6.9 Hz, 2H), 5.45 (dt, J = 14.2, 1.3 Hz, 1H), 6.37 (dt, J = 14.2, 6.9 Hz, 1H); 13C NMR (CDCl3) δ –4.1 (CH3 2), 14.1 (CH3), 16.8 (C), 22.7 (CH2), 26.4 (CH3 3), 29.36 (CH2), 29.43 (CH2), 29.6 (CH2 3), 29.9 (CH2), 31.9 (CH2), 33.7 (CH2), 125.7 (CH), 150.3 (CH); MS m/z (relative intensity) 225 (M+ – tBu, 38), 99 (22), 73 (46), 59 (100). (Z)-1- -1- (1i): [108025-31-6]23)

n-C10H21 SiMe2Ph 1i 1a 1H NMR (CDCl3) δ 0.37 (s, 6H), 0.88 (t, J = 6.9 Hz, 3H), 1.19–1.35

(m, 16H), 2.03 (q, J = 7.0 Hz, 2H), 5.61 (br d, J = 14.0 Hz, 1H), 6.43 (dt, J = 14.0, 7.0 Hz, 1H), 7.33–7.35 (m, 3H), 7.54–7.56 (m, 2H); 13C NMR (CDCl3) δ –0.8 (CH3 2), 14.1 (CH3), 22.7 (CH2), 29.3 (CH2), 29.3 (CH2), 29.5 (CH2 2), 29.6 (CH2 2), 31.9 (CH2), 33.8 (CH2), 126.4 (CH), 127.7 (CH 2), 128.7 (CH), 133.7 (CH

2), 139.8 (C), 151.1 (CH); MS m/z (relative intensity) 302 (M+, 2.7), 287 (M+ – Me, 27), 135 (Me2PhSi+, 92), 121 (100). (Z)-1- -1- (1j): [52835-06-0]19)

n-Bu SiMe3 1j 1a 1H NMR (C6D6) δ 0.18 (s, 9H), 0.86 (t, J = 7.1 Hz, 3H), 1.23–1.33

(m, 4H), 2.12 (q, J = 7.0 Hz, 2H), 5.62 (d, J = 14.0 Hz, 1H), 6.34 (dt, J = 14.0, 7.0 Hz, 1H); 13C NMR (CDCl3) δ 0.2 (CH3 3), 14.0 (CH3), 22.4 (CH2), 32.0 (CH2), 33.3 (CH2), 128.7 (CH), 149.3 (CH); MS m/z (relative intensity) 156 (M+, 0.16), 141 (M+ – Me, 81), 73 (Me3Si+, 76), 59 (100). (Z)-2- -1- -1- (1a-D)

n-C10H21 SiMe3

D

1a-D 1- -1- (13a) 24)

13a (1.19 g, 5.00 mmol) Et2O (60 mL) (1.85 mL, 6.85 mmol) 78 Υ (0.95 M in Et2O, 13.2 mL, 12.5 mmol)

2 50 Υsec- (1.00 M in Et2O, 5.50 mL, 5.50 mmol) 50 Υ 1 (35 w% in D2O, 0.1 mL) (1 mL) 1

1 M (50 mL) (50 mL 3)

30

⇩

(Z)-2- -1--1- (1a-D, 0.759 g, 3.15 mmol) 63% ( : 92%D, α : 3%D) 1H NMR

(CDCl3) δ 0.11 (s, 9H), 0.88 (t, J = 6.5 Hz, 3H), 1.26–1.40 (m, 16H), 2.10 (t, J = 6.4 Hz, 2H), 5.45 (br s, 1H); 13C NMR (CDCl3) δ 0.2 (CH3 3), 14.1 (CH3), 22.7 (CH2), 29.34 (CH2), 29.37 (CH2), 29.58 (CH2), 29.61 (CH2 2), 29.75 (CH2), 31.9 (CH2), 33.4 (CH2), 128.5 (CH), 148.9 (CD, 2J(13C-D) = 23.0 Hz); MS m/z (relative intensity) 241 (M+, 0.44), 226 (M+ – Me), 73 (100). Anal. Calcd for 89% of C15H31DSi, 8% of C15H32Si and 3% of C15H30D2Si: C, 74.62; H, 13.75. Found: C, 74.46; H, 13.84. (Z)-1-[( ) ]-1- (1a-D´ �)

n-C10H21 SiMe2CH2D 1a-D �́ ( ) (PhMe2SiCH2Cl)

(0.271 g, 11.0 mmol) ⇩

10 Et2O (20 mL) PhMe2SiCH2Cl (1.85 g, 10.0 mmol) 2 0 Υ (1.81 g, 100 mmol) 10 1 N (30 mL) TBME (20 mL 3)

(40 mL) (40 mL) ⇩ (bath temp., 110 Υ

/ 45 Torr) ( ) (PhMe2SiCH2D, 1.26 g, 8.33 mmol) 83% (>99%D) 1H NMR (CDCl3) δ 0.24–0.28 (m, 8H), including 0.27 (s), 7.34–7.36 (m, 3H), 7.50–7.54 (m, 2H).

PhMe2SiCH2D (1.26 g, 8.33 mmol) (0.737 mL, 8.33 mmol) 11- (1.39 g, 8.33 mmol) THF (18 mL) 0 Υ

(1.66 M in hexanes, 5.02 mL, 8.33 mmol) 30Me2Si(OTf)CH2D 0 Υ

2 (30 mL) TBME (20 mL 3) (50 mL) ⇩

(bath temp., 90 Υ / 0.45 Torr) 1- 1-() -1- (13a-D �́, 1.79 g, 94 w%, 7.06 mmol) 85%

(>99%D) 1H NMR (CDCl3) δ 0.15 (s, 8H), 0.88 (t, J = 6.3 Hz, 3H), 1.27–1.51 (m, 16H), 2.21 (t, J = 7.0 Hz, 2H).

1a-D´ � 1a 13a-D �́ (94 w%) DIBAL-H 82% (>99%D) Bp 80 Υ (bath temp., 0.39 Torr). IR (neat) 2925, 2854, 1248, 839 cm-1; 1H NMR (C6D6) δ 0.17–0.21 (m, 8H), including 0.20 (s), 0.92 (t, J = 6.7 Hz, 3H), 1.29–1.41 (m, 16H), 2.17 (q, J = 7.0 Hz, 2H), 5.64 (d, J = 14.0 Hz, 1H), 6.39 (dt, J = 14.0, 7.0 Hz, 1H); 13C NMR (CDCl3) δ –0.1 (CD, 2J(13C-D) = 17.9 Hz), 0.2 (CH3 2), 14.1 (CH3), 22.7 (CH2), 29.35 (CH2), 29.37 (CH2), 29.59 (CH2), 29.61 (CH2 2), 29.8 (CH2), 31.9 (CH2), 33.6 (CH2), 128.7 (CH), 149.4 (CH); MS m/z (relative intensity) 241 (M+, 0.70), 226 (M+ – Me), 74 (Me2Si+CH2D, 100). Anal. Calcd for C15H31DSi: C, 74.60; H, 13.77. Found: C, 74.57; H, 13.94. (E)-1- -2- (10b): [42599-24-6]25)

PhI

(10.2 g, 10.0 mmol) (2.91 g,

31

10.0 mmol) AIBN (50 mg, 0.3 mmol) (20 mL) 90 Υ 24-78 Υ (3.8 g, 15.0 mmol) THF (10 mL)

30 (30 mL) (30 mL)

TBME (20 mL 3) ⇩

(E)-1- -2- (10b, 2.01 g, 0.87 mmol) 87% (E)-1- -2-( ) (11): [66680-88-4]26)

PhSnBu3

(10.2 g, 10.0 mmol) (2.91 g, 10.0 mmol) AIBN (50 mg, 0.3 mmol) (20 mL) 90 Υ 2

(156 Υ / 0.49 Torr) (E)-1--2-( ) (9, 3.69 g, 9.4 mmol) 94%

Schlenck (0.05 mmol) (0.10

mmol) 1,2- (1.5 mL) (0.50 mmol) (1.00

mmol) 70 Υ ス

り

┘ 2-[ ( ) ]-1- (2a)

Ph

OSiMe3

n-C10H21 Bp 180 °C (bath temp., 8.0 Torr). IR (neat) 1252, 1090, 1066 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.88

(t, J = 6.4 Hz, 3H), 1.20–1.40 (m, 16H), 1.75 (dt, J = 15.5, 7.5 Hz, 1H), 1.92 (dt, J = 15.5, 7.5 Hz, 1H), 4.88 (s, 1H), 5.11 (s, 1H), 5.14 (s, 1H), 7.22–7.34 (m, 5H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.36 (CH2), 29.46 (CH2), 29.52 (CH2), 29.61 (CH2 2), 30.8 (CH2), 31.9 (CH2), 78.0 (CH), 109.8 (CH2), 126.5 (CH 2), 127.0 (CH), 127.9 (CH 2), 143.1 (C), 151.7 (C); MS m/z (relative intensity) 346 (M+, 16), 73 (100). Anal. Calcd for C22H38OSi: C, 76.23; H, 11.05. Found: C, 76.13; H, 11.21. 2-[(1- )( ) ]-1- (2b)

OSiMe3


(t, J = 6.9 Hz, 3H), 1.23–1.35 (m, 16H), 1.83 (dt, J = 15.8, 7.9 Hz, 1H), 1.98 (dt, J = 15.8, 7.9 Hz, 1H), 4.96

32

(s, 1H), 5.13 (s, 1H), 5.76 (s, 1H), 7.42–7.48 (m, 3H), 7.63 (d, J = 6.8 Hz, 1H), 7.76 (d, J = 8.1 Hz, 1H), 7.82–7.86 (m, 1H), 8.13–8.17 (m, 1H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.9 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 31.9 (CH2), 32.0 (CH2), 75.6 (CH), 110.9 (CH2), 124.3 (CH), 125.19 (CH), 125.24 (CH 2), 125.4 (CH), 127.9 (CH), 128.6 (CH), 130.9 (C), 133.8 (C), 138.3 (C), 151.2 (C); MS m/z (relative intensity) 396 (M+, 23), 73 (100). Anal. Calcd for C26H40OSi: C, 78.72; H, 10.16. Found: C, 78.55; H, 10.35. 2-[(4- )( ) ]-1- (2c)

OSiMe3

n-C10H21O2N

Bp 180 °C (bath temp., 0.80 Torr). IR (neat) 1523, 1348, 1252, 1086 cm–1; 1H NMR (CDCl3) δ 0.12 (s, 9H), 0.87 (t, J = 6.4 Hz, 3H), 1.20–1.40 (m, 16H), 1.69 (dt, J = 16.5, 7.6 Hz, 1H), 1.92 (dt, J = 16.5, 7.6 Hz, 1H), 4.94 (s, 1H), 5.17 (s, 1H), 5.20 (s, 1H), 7.51 (d, J = 8.5 Hz, 2H), 8.16 (d, J = 8.5 Hz, 2H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 14.1 (CH3), 22.6 (CH2), 27.6 (CH2), 29.3 (CH2), 29.4 (CH2), 29.4 (CH2), 29.5 (CH2 2), 30.1 (CH2), 31.9 (CH2), 77.7 (CH), 111.4 (CH2), 123.3 (CH 2), 127.0 (CH 2), 147.1 (C), 150.6 (C), 150.8 (C); MS m/z (relative intensity) 391 (M+, 1.1), 374 (M+ – Me, 7.7), 73 (100). Anal. Calcd for C22H37NO3Si: C, 67.47; H, 9.52; N 3.58. Found: C, 67.57; H, 9.63; N, 3.66. 4-(2- -1- -2- ) (2d)

OSiMe3

n-C10H21MeO2C

Bp 180 °C (bath temp., 0.50 Torr). IR (neat) 1728, 1277, 1109, 1084 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H), 0.87 (t, J = 6.9 Hz, 3H), 1.20–1.32 (m, 16H), 1.72 (dt, J = 15.8, 7.9 Hz, 1H), 1.92 (dt, J = 15.8, 7.9 Hz, 1H), 3.90 (s, 3H), 4.90 (d, J = 1.5 Hz, 1H), 5.16 (s, 2H), 7.40 (d, J = 8.3 Hz, 2H), 7.97 (d, J = 8.3 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.6 (CH2), 29.31 (CH2), 29.39 (CH2), 29.45 (CH2), 29.56 (CH2 2), 30.5 (CH2), 31.9 (CH2), 52.0 (CH3), 77.9 (CH), 110.6 (CH2), 126.3 (CH 2), 128.8 (C), 129.3 (CH 2), 148.5 (C), 151.1 (C), 167.1 (C); MS m/z (relative intensity) 389 (M+ – Me, 4.0), 73 (100). Anal. Calcd for C24H40O3Si: C, 71.23; H, 9.96. Found: C, 71.27; H, 10.19. 2-[(4- )( ) ]-1- (2e)

OSiMe3

n-C10H21NC

Bp 170 °C (bath temp., 0.63 Torr). IR (neat) 2229, 1252, 1084 cm–1; 1H NMR (CDCl3) δ 0.11 (s, 9H), 0.88 (t, J = 6.4 Hz, 3H), 1.20–1.30 (m, 16H), 1.68 (dt, J = 16.2, 8.1 Hz, 1H), 1.90 (dt, J = 16.2, 8.1 Hz, 1H), 4.92 (d, J = 1.2 Hz, 1H), 5.15 (s, 2H), 7.45 (d, J = 8.3 Hz, 2H), 7.60 (d, J = 8.3 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.6 (CH2), 29.31 (CH2), 29.37 (CH2), 29.44 (CH2), 29.55 (CH2 2), 30.2 (CH2), 31.9 (CH2), 77.8 (CH), 110.7 (C), 111.2 (CH2), 119.04 (C), 126.9 (CH 2), 131.9 (CH 2), 148.8 (C), 150.7 (C); MS m/z (relative intensity) 371 (M+, 3.5), 356 (M+ – Me, 2.8) 73 (100). Anal. Calcd for C23H37NOSi: C, 74.33; H, 10.04; N, 3.77. Found: C, 74.23; H, 10.12; N, 3.82.

33

2-[(4- )( ) ]-1- (2f)

OSiMe3

n-C10H21Ac

Bp 245 °C (bath temp., 1.3 Torr). IR (neat) 1687, 1606, 1265, 1084 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H), 0.87 (t, J = 6.9 Hz, 3H), 1.20–1.36 (m, 16H), 1.72 (dt, J = 15.6, 7.8 Hz, 1H), 1.92 (dt, J = 15.6, 7.8 Hz, 1H), 2.59 (s, 3H), 4.91 (d, J = 1.5 Hz, 1H), 5.16 (s, 2H), 7.43 (d, J = 8.6 Hz, 2H), 7.90 (d, J = 8.6 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 26.6 (CH2), 27.7 (CH3), 29.31 (CH2), 29.40 (CH2), 29.46 (CH2), 29.56 (CH2 2), 30.5 (CH2), 31.9 (CH2), 77.8 (CH), 110.7 (CH2), 126.5 (CH 2), 128.2 (CH2), 136.0 (C), 148.8 (C), 151.1 (C), 197.9 (C); MS m/z (relative intensity) 388 (M+, 9.5), 73 (100). Anal. Calcd for C24H40O2Si: C, 74.17; H, 10.37. Found: C, 73.99; H, 10.39. 2-[(4- )( ) ]-1- (2g)

OSiMe3

n-C10H21F

Bp 143 °C (bath temp., 0.50 Torr). IR (neat) 1252, 1223, 1080 cm–1; 1H NMR (CDCl3) δ 0.08 (s, 9H), 0.88 (t, J = 6.4 Hz, 3H), 1.21–1.37 (m, 16H), 1.73 (dt, J = 15.8, 7.9 Hz, 1H), 1.90 (dt, J = 15.8, 7.9 Hz, 1H), 4.89 (s, 1H), 5.08 (s, 1H), 5.14 (s, 1H), 6.98 (dd, J = 8.8, 8.8 Hz, 2H), 7.28 (dd, J = 8.8, 5.6 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.32 (CH2), 29.42 (CH2), 29.48 (CH2), 29.58 (CH2 2), 30.7 (CH2), 31.9 (CH2), 77.4 (CH), 110.0 (CH2), 114.7 (CH 2, 2J(13C-19F) = 21.3 Hz), 128.0 (CH

2, 3J(13C-19F) = 7.8 Hz), 138.9 (C, 4J(13C-19F) = 2.8 Hz), 151.5 (C), 161.9 (C, 1J(13C-19F) = 244.7 Hz); MS m/z (relative intensity) 364 (M+, 3.1), 349 (M+ – Me, 2.0), 73 (100). Anal. Calcd for C22H37FOSi: C, 72.47; H, 10.23. Found: C, 72.09; H, 10.29. 2-[(4- )( ) ]-1- (2h)

OSiMe3

n-C10H21Cl

Bp 180 °C (bath temp., 0.55 Torr). IR (neat) 1489, 1252, 1014 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.87 (t, J = 6.4 Hz, 3H), 1.19–1.33 (m, 16H), 1.72 (dt, J = 15.4, 7.4 Hz, 1H), 1.90 (dt, J = 15.4, 7.2 Hz, 1H), 4.88 (s, 1H), 5.08 (s, 1H), 5.20 (s, 1H), 7.26 (s, 4H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.12 (CH3), 22.7 (CH2), 27.7 (CH2), 29.36 (CH2), 29.43 (CH2), 29.51 (CH2), 29.60 (CH2 2), 30.6 (CH2), 31.9 (CH2), 77.5 (CH), 110.2 (CH2), 127.8 (CH 2), 128.1 (CH 2), 132.6 (C), 141.8 (C), 151.3 (C); MS m/z (relative intensity) 382 (M+ + 2, 1.7), 380 (M+, 1.6), 73 (100). Anal. Calcd for C22H37ClOSi: C, 69.34; H, 9.79. Found: C, 69.44; H, 9.87. 2-[(2- )( ) ]-1- (2i)

OSiMe3

n-C10H21

Cl

34

Bp 148 °C (bath temp., 0.56 Torr). IR (neat) 1468, 1441, 1252, 1084 cm–1; 1H NMR (CDCl3) δ 0.07 (s, 9H), 0.88 (t, J = 6.6 Hz, 3H), 1.23–1.42 (m, 16H), 1.86 (dt, J = 15.0, 7.5 Hz, 1H), 1.97 (dt, J = 15.0, 7.5 Hz, 1H), 4.90 (s, 1H), 5.05 (s, 1H), 5.54 (s, 1H), 7.14–7.31 (m, 3H), 7.51 (dd, J = 7.6, 2.0 Hz, 1H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.9 (CH2), 29.33 (CH2), 29.42 (CH2), 29.50 (CH2), 29.60 (CH2 2), 31.8 (CH2), 31.9 (CH2), 73.1 (CH), 110.5 (CH2), 126.7 (CH), 128.3 (CH), 129.0 (CH×2), 132.4 (C), 140.7 (C), 150.3 (C); MS m/z (relative intensity) 382 (M+ + 2, 1.6), 380 (M+, 4.2), 73 (100). Anal. Calcd for C22H37ClOSi: C, 69.34; H, 9.79. Found: C, 69.28; H, 9.94. 2-[(4- )( ) ]-1- (2j)

OSiMe3

n-C10H21Br

Bp 150 °C (bath temp., 0.51 Torr). IR (neat) 1252, 1072, 891, 841 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.88 (t, J = 6.6 Hz, 3H), 1.21–1.33 (m, 16H), 1.72 (dt, J = 15.8, 7.9 Hz, 1H), 1.90 (dt, J = 15.8, 7.9 Hz, 1H), 4.88 (d, J = 1.5 Hz, 1H), 5.06 (s, 1H), 5.12 (s, 1H), 7.20 (d, J = 8.5 Hz, 2H), 7.42 (d, J = 8.5 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.32 (CH2), 29.41 (CH2), 29.48 (CH2), 29.59 (CH2 2), 30.6 (CH2), 31.9 (CH2), 77.5 (CH), 110.3 (CH2), 127.8 (CH 2), 128.2 (CH 2), 131.0 (C), 142.3 (C), 151.3 (C); MS m/z (relative intensity) 426 (M+ + 2, 1.1), 424 (M+, 0.9), 73 (100). Anal. Calcd for C22H37BrOSi: C, 62.10; H, 8.76. Found: C, 62.26; H, 8.85. 2-[(4- )( ) ]-1- (2k)

OSiMe3

n-C10H21I

Bp 159 °C (bath temp., 0.50 Torr). IR (neat) 1252, 1082, 1007 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.88 (t, J = 6.4 Hz, 3H), 1.21–1.33 (m, 16H), 1.72 (dt, J = 16.4, 8.2 Hz, 1H), 1.90 (dt, J = 16.4, 8.2 Hz, 1H), 4.88 (s, 1H), 5.05 (s, 1H), 5.12 (s, 1H), 7.08 (d, J = 8.4 Hz, 2H), 7.62 (d, J = 8.4 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 30.5 (CH2), 31.9 (CH2), 77.6 (CH), 92.4 (C), 110.3 (CH2), 128.5 (CH 2), 137.0 (CH 2), 143.0 (C), 151.3 (C); MS m/z (relative intensity) 472 (M+, 1.7), 75 (100), 73 (39). Anal. Calcd for C22H37IOSi: C, 55.92; H, 7.89. Found: C, 55.94; H, 7.86. 2-[(4- )( ) ]-1- (2l)

OSiMe3

n-C10H21Me

Bp 165 °C (bath temp., 0.50 Torr). IR (neat) 1252, 1080, 895, 841 cm–1; 1H NMR (CDCl3) δ 0.08 (s, 9H), 0.88 (t, J = 6.9 Hz, 3H), 1.21–1.38 (m, 16H), 1.75 (dt, J = 15.7, 7.4 Hz, 1H), 1.92 (dt, J = 15.7, 7.4 Hz, 1H), 2.32 (s, 3H), 4.87 (s, 1H), 5.07 (s, 1H), 5.14 (s, 1H), 7.10 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 14.1 (CH3), 21.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.33 (CH2), 29.45 (CH2), 29.51 (CH2), 29.60 (CH2 2), 30.9 (CH2), 31.9 (CH2), 77.8 (CH), 109.5 (CH2), 126.4 (CH 2), 128.7 (CH2), 136.5 (C), 140.2 (C), 151.8 (C); MS m/z (relative intensity) 360 (M+, 3.0), 345 (M+ – Me, 16), 73 (100).

35

Anal. Calcd for C23H40OSi: C, 76.60; H, 11.18. Found: C, 76.44; H, 10.98. 2-[(4- )( ) ]-1- (2m)

OSiMe3

n-C10H21MeO

Bp 183 °C (bath temp., 0.79 Torr). IR (neat) 1510, 1250, 1080, 895, 841 cm–1; 1H NMR (CDCl3) δ 0.08 (s, 9H), 0.88 (t, J = 6.5 Hz, 3H), 1.22–1.38 (m, 16H), 1.76 (dt, J = 15.0, 7.5 Hz, 1H), 1.91 (dt, J = 15.0, 7.5 Hz, 1H), 3.80 (s, 3H), 4.87 (s, 1H), 5.06 (s, 1H), 5.14 (s, 1H), 6.83 (d, J = 8.6 Hz, 2H), 7.23 (d, J = 8.6 Hz, 2H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.33 (CH2), 29.46 (CH2), 29.51 (CH2), 29.59 (CH2 2), 31.0 (CH2), 31.9 (CH2), 55.2 (CH3), 77.4 (CH), 109.4 (CH2), 113.3 (CH 2), 127.7 (CH 2), 135.3 (C), 151.9 (C), 158.6 (C); MS m/z (relative intensity) 376 (M+, 0.52), 361 (M+ – Me, 0.41), 159 (100). Anal. Calcd for C23H40O2Si: C, 73.34; H, 10.70. Found: C, 73.01; H, 10.70. 2-[(4- )( ) ]-1- (2n)

OSiMe3

n-C10H21AcO

Bp 208 °C (bath temp., 0.48 Torr). IR (neat) 1768, 1200 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.88 (t, J = 6.1 Hz, 3H), 1.22–1.38 (m, 16H), 1.74 (dt, J = 15.4, 7.7 Hz, 1H), 1.92 (dt, J = 15.4, 7.7 Hz, 1H), 2.29 (s, 3H), 4.88 (s, 1H), 5.11 (s, 1H), 5.14 (s, 1H), 7.02 (d, J = 8.7 Hz, 2H), 7.33 (d, J = 8.7 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 21.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 30.6 (CH2), 31.9 (CH2), 77.6 (CH), 110.0 (CH2), 120.9 (CH 2), 127.4 (CH 2), 140.7 (C), 149.6 (C), 151.5 (C), 169.4 (C); MS m/z (relative intensity) 404 (M+, 1.5), 389 (M+ – Me, 3.5), 345 (M+ – AcO, 30) 73 (100). Anal. Calcd for C22H44OSi: C, 71.23; H, 9.96. Found: C, 71.22; H, 10.10. 2-[2- -1-( ) ]-1- (2o)

OSiMe3

n-C10H21 Bp 190 Υ (bath temp., 0.50 Torr). IR (neat) 1250, 1068, 887, 841 cm-1; 1H NMR (CDCl3) δ 0.07 (s, 9H),

0.80-0.90 (m, 9H), 1.18–1.55 (m, 21H), 1.75 (dt, J = 16.9, 7.9 Hz, 1H), 1.92 (dt, J = 16.9, 7.9 Hz, 1H), 3.93 (d, J = 5.9 Hz, 1H), 4.83 (d, J = 1.6 Hz, 1H), 4.92 (s, 1H); 13C NMR (CDCl3) δ 0.19 (CH3 3), 10.91 (CH3), 11.07 (CH3), 14.12 (CH3), 20.18 (CH2), 21.52 (CH3), 22.69 (CH2), 27.78 (CH2), 29.35 (CH2), 29.60 (CH2), 29.65 (CH2 2), 29.70 (CH2), 30.50 (CH2), 31.91 (CH2), 43.63 (CH), 78.29 (CH), 110.18 (CH2), 150.95 (C); MS m/z (relative intensity) 340 (M+, 1), 269 (31), 143 (76), 73 (100). Anal. Calcd for C21H44OSi: C, 74.04; H, 13.02. Found: C, 74.05; H, 13.14. 2-[ ( ) ]-1- (2p)

OSiMe3

n-C10H21 Bp 175 °C (bath temp., 0.35 Torr). IR (neat) 2360, 1250, 1063, 841 cm–1; 1H NMR (CDCl3) δ 0.07 (s, 9H),

36

0.77–0.90 (m, 5H) including 0.88 (t, J = 6.3 Hz), 1.07–1.92 (m, 26H), 2.05 (dt, J = 16.0, 7.9 Hz, 1H), 3.67 (d, J = 7.6 Hz, 1H), 4.79 (d, J = 1.6 Hz, 1H), 4.84 (s, 1H); 13C NMR (CDCl3) δ –0.2 (CH3 3), 14.1 (CH3), 22.7 (CH2), 26.1 (CH2), 26.3 (CH2), 26.6 (CH2), 27.8 (CH2), 29.0 (CH2), 29.3 (CH2), 29.62 (CH2), 29.65 (CH2 2), 29.72 (CH2), 29.88 (CH2 2), 31.9 (CH2), 41.0 (CH), 82.3 (CH), 110.3 (CH2), 150.6 (C); MS m/z (relative intensity) 352 (M+, 5), 269 (M+ – C6H11, 31), 143 (100), 73 (99). Anal. Calcd for C22H44OSi: C, 74.92; H, 12.58. Found: C, 74.86; H, 12.62. 2- -4- -3-( )-1,4- (2q)

OSiMe3

n-C10H21 Bp 118 °C (bath temp., 10 Torr). IR (neat) 1252, 1090, 901, 841 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H),

0.88 (t, J = 6.8 Hz, 3H), 1.26–1.46 (m, 16H), 1.59 (s, 3H), 1.78–2.00 (m, 2H), 4.43 (s, 1H), 4.86 (s, 2H), 4.99 (t, J = 1.1 Hz, 1H), 5.08 (s, 1H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 17.6 (CH3), 22.7 (CH2), 27.9 (CH2), 29.35 (CH2), 29.58 (CH2 2), 29.64 (CH2 2), 31.1 (CH2), 31.9 (CH2), 79.4 (CH), 109.8 (CH2), 111.6 (CH2), 145.9 (C) 149.6 (C); MS m/z (relative intensity) 310 (M+, 1.5), 295 (M+ – Me, 5.3), 73 (100). Anal. Calcd for C19H38OSi: C, 73.47; H, 12.33. Found: C, 73.18; H, 12.19. 2- -3- -3-( ) (2r) : [83205-05-4]

Ph

OSiMe3

Me Bp 75 °C (bath temp., 1.3 Torr). IR (neat) 2958, 1252, 1092, 1066 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H),

1.55 (s, 3H), 4.87 (t, J = 1.5 Hz, 1H), 5.10 (br s, 2H), 7.20–7.36 (m, 5H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 17.4 (CH3), 78.3 (CH), 111.2 (CH2), 126.2 (CH 2), 126.9 (CH), 128.0 (CH 2), 142.9 (C), 147.6 (C); MS m/z (relative intensity) 220 (M+, 8.7), 205 (M+ – Me, 25), 73 (100). Anal. Calcd for C13H20OSi: C, 70.85; H, 9.15. Found: C, 71.02; H, 8.87. 2- -3- -3-( ) (2r �́)

OSiMe3

MeCl

Bp 90 °C (bath temp., 1.3 Torr). IR (neat) 1491, 1252, 1086, 891 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H), 1.52 (s, 3H), 4.87 (t, J = 1.5 Hz, 1H), 5.07 (s, 2H), 7.27 (s, 4H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 17.2 (CH3), 77.7 (CH), 111.7 (CH2), 127.6 (CH 2), 128.1 (CH 2), 132.6 (C), 141.6 (C), 147.2 (C); MS m/z (relative intensity) 256 (M++2, 1.9), 254 (M+, 6.2), 73 (100). Anal. Calcd for C13H19ClOSi: C, 61.27; H, 7.52. Found: C, 61.34; H, 7.53. 2- -3- -3-( ) (2s)

Ph

OSiMe3

37

Bp 110 °C (bath temp., 0.9 Torr). IR (neat) 2925, 2852, 1252 cm–1; 1H NMR (CDCl3) δ 0.08 (s, 9H), 1.01–1.26 (m, 5H), 1.54–1.80 (m, 6H), 4.93 (s, 1H), 5.13 (s, 1H), 5.15 (t, J = 1.5 Hz, 1H), 7.20–7.33 (m, 5H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 26.3 (CH2), 26.8 (CH2), 26.9 (CH2), 33.3 (CH2), 34.2 (CH2), 39.7 (CH), 77.2 (CH), 108.6 (CH2), 126.9 (CH 2), 127.0 (CH), 127.9 (CH 2), 143.1 (C), 157.1 (C); MS m/z (relative intensity) 288 (M+, 16), 205 (M+ – C6H11, 52), 73 (100). Anal. Calcd for C18H28OSi: C, 74.94; H, 9.78. Found: C, 74.90; H, 9.68. 2,3- -3-( ) (2t)

Ph

OSiMe3

Ph Bp 120 °C (bath temp., 1.3 Torr). IR (neat) 1252, 1066, 698 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H), 5.41 (s,

1H), 5.48 (s, 1H), 5.60 (s, 1H), 7.15–7.34 (m, 10H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 76.8 (CH), 114.0 (CH2), 126.8 (CH 2), 127.1 (CH), 127.2 (CH), 127.3 (CH 2), 127.9 (CH 2), 128.1 (CH 2), 139.7 (C), 142.7 (C), 150.9 (C); MS m/z (relative intensity) 282 (M+, 2.6), 267 (M+ – Me, 1.5), 73 (100). Anal. Calcd for C18H22OSi: C, 76.54; H, 7.85. Found: C, 76.71; H, 7.74. 3- -3-[4-( ) ]-3-( ) (2u)

F3C

Ph

Me3SiO

Bp 106 °C (bath temp., 0.82 Torr). IR (neat) 1327, 1254, 1068 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H), 5.46

(s, 1H), 5.56 (s, 1H), 5.59 (s, 1H), 7.20–7.32 (m, 5H), 7.36 (d, J = 8.4 Hz, 2H), 7.45 (d, J = 8.4 Hz, 2H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 76.9 (CH), 115.8 (CH2), 124.2 (C, 1J(13C-19F) = 271.9 Hz) 124.8 (CH 2, 3J(13C-19F) = 3.9 Hz), 126.6 (CH 2), 127.3 (CH), 127.7 (CH 2), 128.2 (CH 2), 129.2 (C, 2J(13C-19F) = 32.5 Hz), 142.1 (C), 143.1 (C), 149.9 (C); MS m/z (relative intensity) 350 (M+, 1.2), 335 (M+ – Me, 4.5), 179 (100), 73 (64). Anal. Calcd for C19H21F3OSi: C, 65.12; H, 6.04. Found: C, 64.86; H, 6.11. 2-[(t- )( ) ]-1- (2v)

Ph

OSiMe2t-Bu


(s, 3H), 0.91 (s, 12H) including 0.88 (t, J = 6.9 Hz), 1.14–1.32 (m, 16H), 1.73 (dt, J = 15.8, 8.0 Hz, 1H), 1.91 (dt, J = 15.8, 8.0 Hz, 1H), 4.84 (s, 1H), 5.11 (s, 1H), 5.17 (s, 1H), 7.23–7.34 (m, 5H); 13C NMR (CDCl3) δ –5.0 (CH3), –4.9 (CH3), 14.1 (CH3), 18.3 (C), 22.7 (CH2), 25.8 (CH3 3), 27.7 (CH2), 29.32 (CH2), 29.45 (CH2), 29.49 (CH2), 29.57 (CH2 2), 30.4 (CH2), 31.9 (CH2), 78.4 (CH), 109.4 (CH2), 126.3 (CH 2), 126.8 (CH), 127.9 (CH 2), 143.5 (C), 152.0 (C); MS m/z (relative intensity) 331 (M+ – C4H9, 61), 75 (100). Anal. Calcd for C25H44OSi: C, 77.25; H, 11.41. Found: C, 77.16; H, 11.20. 2-[( )( ) ]-1- (2w)

Ph

OSiMe2Ph

n-C10H21 Bp 188 °C (bath temp., 0.43 Torr). IR (neat) 1252, 1088, 1065, 698 cm–1; 1H NMR (CDCl3) d 0.31 (s, 3H),

38

0.35 (s, 3H), 0.88 (t, J = 6.4 Hz, 3H), 1.15–1.35 (m, 16H), 1.72 (dt, J = 15.5, 7.5 Hz, 1H), 1.90 (dt, J = 15.5, 7.5 Hz, 1H), 4.87 (s, 1H), 5.11 (s, 1H), 5.16 (s, 1H), 7.19–7.31 (m, 5H), 7.33–7.37 (m, 3H), 7.53–7.56 (m, 2H); 13C NMR (CDCl3) d –1.16 (CH3), –1.13 (CH3), 14.1 (CH3), 22.7 (CH2), 27.6 (CH2), 29.32 (CH2), 29.40 (CH2), 29.48 (CH2), 29.59 (CH2 2), 30.8 (CH2), 31.9 (CH2), 78.3 (CH), 109.8 (CH2), 126.5 (CH 2), 127.0 (CH), 127.7 (CH 2), 127.9 (CH 2), 129.5 (CH), 133.6 (CH 2), 137.9 (C), 142.9 (C), 151.4 (C); MS m/z (relative intensity) 408 (M+, 10), 135 (100). Anal. Calcd for C27H40OSi: C, 79.35; H, 9.87. Found: C, 79.04; H, 9.77. 2-[ ( ) ]-1- (2y)

Ph

OSiMe3

n-Bu Bp 79 °C (bath temp., 0.38 Torr). IR (neat) 1252, 1066 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.83 (t, J =

7.2 Hz, 3H), 1.17–1.40 (m, 4H), 1.76 (dt, J = 15.4, 7.7 Hz, 1H), 1.94 (dt, J = 15.4, 7.7 Hz, 1H), 4.89 (d, J = 1.6 Hz, 1H), 5.12 (s, 1H), 5.15 (q, J = 0.8 Hz, 1H), 7.20–7.35 (m, 5H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.0 (CH3), 22.5 (CH2), 29.9 (CH2), 30.5 (CH2), 78.0 (CH), 109.8 (CH2), 126.5 (CH 2), 126.9 (CH), 127.9 (CH 2), 143.1 (C), 151.7 (C); MS m/z (relative intensity) 262 (M+, 18), 73 (100). Anal. Calcd for C16H26OSi: C, 73.22; H, 9.98. Found: C, 72.97; H, 10.23. 2-[ ( ) ]-1- (2z)

Ph

OSiEt3

n-C10H21 Bp 203 °C (bath temp., 0.61 Torr). IR (neat) 1458, 1090 cm–1; 1H NMR (CDCl3) δ 0.58 (q, J = 8.3 Hz, 9H),

0.85–0.93 (m, 12H), 1.14–1.36 (m, 16H), 1.73 (dt, J = 16.1, 8.1 Hz, 1H), 1.92 (dt, J = 16.1, 8.1 Hz, 1H), 4.85 (s, 1H), 5.12 (s, 1H), 5.19 (s, 1H), 7.20–7.36 (m, 5H); 13C NMR (CDCl3) δ 4.8 (CH2 3), 6.8 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 30.5 (CH2), 31.9 (CH2), 78.0 (CH), 109.3 (CH2), 126.3 (CH 2), 126.9 (CH), 127.9 (CH 2), 143.5 (C), 152.0 (C); MS m/z (relative intensity) 388 (M+, 6.7), 359 (M+ – Et, 29), 129 (100), 103 (21). Anal. Calcd for C25H44OSi: C, 77.25; H, 11.41. Found: C, 77.29; H, 11.28. 1- -2-[ ( ) ]-1- (2a-D)

Ph

OSiMe3

n-C10H21

D

1a-D (1.00 mmol) (0.50 mmol)

2a-D 87% (86%D) Bp 128 °C (bath temp., 0.46 Torr). IR (neat) 1252, 1090, 1066 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.88 (t, J = 6.4 Hz, 3H), 1.21–1.34 (m, 16H), 1.75 (dt, J = 15.8, 7.9 Hz, 1H), 1.92 (dt, J = 15.8, 7.9 Hz, 1H), 4.87 (s, 0.41H), 5.11 (s,1H), 5.13 (s, 0.70H), 7.20–7.34 (m, 5H); 13C NMR (CDCl3) δ 0.0 (CH3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 30.8 (CH2), 31.9 (CH2), 78.0 (CH), 109.5 (CD, 2J(13C-D) = 24.6 Hz), 126.5 (CH 2), 127.0 (CH), 127.9 (CH

2), 143.1 (C), 151.6 (C); MS m/z (relative intensity) 347 (M+, 5.5), 73 (100). Anal. Calcd for 83% of C22H37DOSi, 14% of C22H38OSi and C22H36D2OSi: C, 76.04; H, 11.28. Found: C, 75.91; H, 11.44. 2-[( ) ] ]-1- (2a-D’)

39

Ph

OSiMe2CH2D

n-C10H21 Bp 125 °C (bath temp., 0.53 Torr). IR (neat) 1252, 1090, 1067 cm–1; 1H NMR (CDCl3) δ 0.06–0.09 (m,

8H) including 0.09 (s), 0.87 (t, J = 6.6 Hz, 3H), 1.21–1.36 (m, 16H), 1.75 (dt, J = 15.8, 7.9 Hz, 1H), 1.92 (dt, J = 15.8, 7.9 Hz, 1H), 4.88 (s, 1H), 5.11 (s, 1H), 5.15 (s, 1H), 7.20–7.34 (m, 5H); 13C NMR (CDCl3) δ –0.2 (CD, 2J(C-D) = 17.9 Hz), 0.0 (CH3 2), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 30.8 (CH2), 31.9 (CH2), 78.0 (CH), 109.8 (CH2), 126.5 (CH 2), 127.0 (CH), 127.9 (CH 2), 143.1 (C), 151.7 (C); MS m/z (relative intensity) 347 (M+, 20), 74 (100). Anal. Calcd for C22H37DOSi: C, 76.01; H, 11.31. Found: C, 76.04; H, 11.40. 2-[( ) ] ]-1- (2y-D’)

Ph

OSiMe2CH2D

n-Bu Bp 85 °C (bath temp., 0.75 Torr). IR (neat) 1252, 1066 cm–1; 1H NMR (CDCl3) δ 0.06–0.11 (m, 8H)

including 0.09 (s), 0.83 (t, J = 7.1 Hz, 3H), 1.17–1.40 (m, 4H), 1.76 (dt, J = 15.6, 7.8 Hz, 1H), 1.94 (dt, J = 15.6, 7.8 Hz, 1H), 4.88 (s, 1H), 5.11 (s, 1H), 5.15 (q, J = 0.8 Hz, 1H), 7.20–7.34 (m, 5H); 13C NMR (CDCl3) δ –0.3 (CD, 2J(C-D) = 17.9 Hz), 0.0 (CH3 2), 14.0 (CH3), 22.5 (CH2), 29.9 (CH2), 30.5 (CH2), 78.0 (CH), 109.8 (CH2), 126.5 (CH 2), 127.0 (CH), 127.9 (CH 2), 143.1 (C), 151.7 (C); MS m/z (relative intensity) 263 (M+, 18), 74 (100). Anal. Calcd for C16H25DOSi: C, 72.94; H, 10.33. Found: C, 72.67; H, 10.41. 2-( )-1- (3a)

Ph

OMe

n-C10H21 Bp 175 °C (bath temp., 0.57 Torr). IR (neat) 1452, 1097 cm–1; 1H NMR (CDCl3) δ 0.88 (t, J = 6.8 Hz, 3H),

1.22–1.40 (m, 16H), 1.80 (dt, J = 16.2, 8.1 Hz, 1H), 1.91 (dt, J = 16.2, 8.1 Hz, 1H), 3.32 (s, 3H), 4.59 (s, 1H), 4.98 (d, J = 1.5 Hz, 1H), 5.17 (s, 1H), 7.22–7.33 (m, 5H); 13C NMR (CDCl3) δ 14.1 (CH3), 22.7 (CH2), 27.6 (CH2), 29.32 (CH2), 29.42 (CH2), 29.48 (CH2), 29.58 (CH2 2), 31.1 (CH2), 31.9 (CH2) 56.6 (CH3), 86.8 (CH), 111.0 (CH2), 126.8 (CH 2), 127.4 (CH), 128.1 (CH 2), 140.6 (C), 149.1 (C); MS m/z (relative intensity) 288 (M+, 14), 147 (66), 121 (100). Anal. Calcd for C20H32O: C, 83.27; H, 11.18. Found: C, 83.12; H, 11.36. 2-[ (4- ) ]-1- (3b)

OMe

n-C10H21Cl

Bp 178 °C (bath temp., 0.67 Torr). IR (neat) 1491, 1466, 1092 cm–1; 1H NMR (CDCl3) δ 0.88 (t, J = 6.9 Hz, 3H), 1.21–1.41 (m, 16H), 1.75 (dt, J = 15.6, 7.8 Hz, 1H), 1.88 (dt, J = 15.6, 7.8 Hz, 1H), 3.31 (s, 3H), 4.56 (s, 1H), 4.99 (d, J = 1.5 Hz, 1H), 5.15 (s, 1H), 7.27 (s, 4H); 13C NMR (CDCl3) δ 14.1 (CH3), 22.7 (CH2), 27.5 (CH2), 29.32 (CH2), 29.41 (CH2), 29.47 (CH2), 29.59 (CH2 2), 30.8 (CH2), 31.9 (CH2) 56.6 (CH3), 86.2 (CH), 111.7 (CH2), 128.1 (CH 2), 128.3 (CH 2), 133.0 (C), 139.2 (C), 148.7 (C); MS m/z (relative intensity) 324 (M+ + 2, 0.34), 322 (M+, 1.1), 163 (100). Anal. Calcd for C20H31ClO: C, 74.39; H, 9.68. Found: C, 74.25; H, 9.92.

40

2-{[2-( ) ] }-1- (3c) 3-{[2-(

) ] }-1- (4c) (3c:4c = 91:9)

Ph

O

n-C10H21

OSiMe3

Ph

O

n-C9H19

OSiMe3

3c 4c Bp 165 Υ (bath temp, 0.70 Torr). IR (neat) 1250, 1099, 843 cm-1; 1H NMR (CDCl3) for 3c δ 0.12 (s, 9H),

0.88 (t, J = 7.1 Hz, 3H), 1.21-1.36 (m, 16H), 1.80 (dt, J = 15.5, 7.8 Hz, 1H), 1.92 (dt, J = 15.5, 7.8 Hz, 1H), 3.45 (dt, J = 11.0, 5.6 Hz, 1H), 3.53 (dt, J = 11.0, 5.6 Hz, 1H), 3.76 (t, J = 5.6 Hz, 2H), 4.75 (s, 1H), 4.96 (s, 1H), 5.16 (s, 1H), 7.22-7.35 (m, 5H); 13C NMR (CDCl3) for 3c δ –0.43 (CH3 3), 14.12 (CH3), 22.67 (CH2), 27.51 (CH2), 29.32 (CH2), 29.45 (CH2), 29.50 (CH2), 29.58 (CH2 2), 30.99 (CH2), 31.90 (CH2), 62.03 (CH2), 69.87 (CH2), 85.31 (CH), 111.11 (CH2), 126.89 (CH 2), 127.25 (CH), 128.02 (CH 2), 140.78 (C), 149.34 (C); MS m/z (rel intensity) 390 (M+, 9), 347 (21), 117 (95), 73 (100). Anal. Calcd for C24H42O2Si: C, 73.78; H, 10.84. Found: C, 73.77; H, 10.82. 1- (8): [3482-63-1]27)

n-C10H21

OMe

1H NMR (CDCl3) δ 0.87 (t, J = 6.6 Hz, 3H), 1.19-1.42 (m, 20H), 3.33 (s, 3H), 3.36 (t, J = 6.7 Hz); 13C

NMR (CDCl3) δ 14.1 (CH3), 22.7 (CH2), 26.1 (CH2), 29.3 (CH2), 29.51 (CH2), 29.60 (CH2 2), 29.64 (CH2), 29.66 (CH2 2), 31.9 (CH2), 58.5 (CH3), 72.97 (CH2).

41

1) ∟ 2004, 280. 2) (a) Jin, H.; Uenishi, J.; Christ, W. J.; Kishi, Y. J. Am. Chem. Soc. 1986, 108, 5644. (b) Takai, K.;

Tagashira, M.; Kuroda, T.; Oshima, K.; Utimoto, K.; Nozaki, H. J. Am. Chem. Soc. 1986, 108, 6048. (c) Takai, K.; Kimura, K.; Kuroda, T.; Hiyama, T.; Nozaki, H. Tetrahedron Lett. 1983, 24, 5281.

3) Kishi, Y.; Suh, E. M. J. Am. Chem. Soc. 1994, 116, 11205. 4) (a) Rowley, M.; Tsukamoto, M.; Kishi, Y. J. Am. Chem. Soc. 1989, 111, 2735. (b) MacMillan, D. W. C.;

Overman, L. E. J. Am. Chem. Soc. 1995, 117, 10391. 5) (a) Oblinger, E.; Montgomery, J. J. Am. Chem. Soc. 1997, 119, 9065. (b) Huang, W.-S.; Chan, J.;

Jamison, T. F. Org. Lett. 2000, 2, 4221. (c) Miller, K. M.; Huang, W.-S.; Jamison, T. F. J. Am. Chem. Soc. 2003, 125, 3442. (c) Montgomery, J. Angew. Chem. Int. Ed. 2004, 43, 3890. (d) Moslin, R. M.; Miller-Moslin, K.; Jamison, T. F. Chem. Comm. 2007, 43, 4441.

6) (a) Ng, S.-S.; Jamison, T. F. J. Am. Chem. Soc. 2005, 127, 14194. (b) Ng, S.-S.; Ho, C.-Y.; Jamison, T. F. J. Am. Chem. Soc. 2006, 128, 11513.

7) Brook, M. A. Silicon in Organic, Organomtallic, and Polymer Chemistry; Wiley: New York, 2000; pp 571-575.

8) Denmark, S. E.; Sweos, R. F. Organosilicon compounds in Cross-coupling Reactions. In Metal-catalyzed Cross-coupling Reactions, 2nd Ed.; de Meijere, A.; Diedrich, F., Eds.; Wiley-VCH: Weinheim, 2004; Chap. 4, pp163-216.

9) (a) Tius, M. A.; Ali, S. J. Org. Chem. 1982, 47, 3163. (b) Blumekopf, T. A.; Bratz, M.; Castañeda, A.; Look, G. C.; Overman, L. E.; Rodriguez, D.; Thompson, A. S. J. Am. Chem. Soc. 1990, 112, 4386. (c) Blumenkopt, T. A.; Look, G. C.; Overman, L. E. J. Am. Chem. Soc. 1990, 112, 4399.

10) Ikenaga, K.; Kikukawa, K.; Matsuda, T. J. Chem. Soc. Perkin. Trans. I 1986, 1959. 11) Miura, K.; Itaya, R.; Horiike, M.; Izumi, H.; Hosomi, A. Synlett 2005, 3148. 12) Schils, R.; Simal, F.; Dermonceau, A.; Noels, A. F.; Eremenko, I. L.; Sidorov, A. A.; Nefedov, S. E.

Tetrahedron Lett. 1998, 39, 7849. 13) Bell, R. A.; Chisholm, M. H.; Couch, D. A.; Rankel, L. A. Inorg. Chem. 1977, 16, 677. 14) (a) Voronkov, M. G.; Druzhdzh, P. V.; Pukhnarevich, V. B. Zh. Obshch. Khim. 1980, 50, 1662; Chem.

Abstr. 1980, 93, 220825h. (b) Voronkov, M. G.; Ushakova, N. I.; Tsykhanskaya, I. I.; Pukhnarevich, V. B. J. Organomet. Chem. 1984, 264, 39. (c) Voronkov, M. G.; Pukhnarevich, V. B.; Ushakova, N. I.; Tsykhanskaya, I. I.; Albanov, A. I.; Vitkovskii, V. Yu. Zh. Obshch. Khim. 1985, 55, 94; Chem. Abstr. 1985, 103, 6399d.

15) (a) Gilges, H.; Schubert, U. Organometallics 1998, 17, 4760. (b) Müller, C.; Lachicotte, R. J.; Jones, W. D. Organometallics 2002, 21, 1190.

16) Kataoka, Y.; Takai, K.; Oshima, K.; Utimoto, K. J. Org. Chem. 1992, 57, 1615. 17) Taniguchi, M.; Nozaki, K.; Miura, K.; Oshima, K.; Utimoto, K. Bull. Chem. Soc. Jpn. 1992, 65, 349. 18) Soderquist, J. A.; Lee, S. J. H. Tetrahedron 1988, 44, 4033. 19) Concellon, J. M.; Bernad, P. L.; Bardales, E. Org. Lett. 2001, 3, 937. 20) (a) Miller, K. M.; Luanphaisarnnont, T.; Molinaro, C.; Jamison, T. F. J. Am. Chem. Soc. 2004, 126, 4130.

(b) Desai, N. B.; McKelvie, N. J. Am. Chem. Soc. 1962, 84, 1745. 21) Rim, C.; Son, D. Y. Org. Lett. 2003, 5, 3443. 22) Sudo, T.; Asao, N.; Gevorgyan, V.; Yamamoto, Y. J. Org. Chem. 1999, 64, 2494. 23) Miura, K.; Oshima, K.; Utimoto, K. Bull. Chem. Soc. Jpn. 1993, 66, 2356. 24) Urabe, H.; Hamada, T.; Sato, F. J. Am. Chem. Soc. 1999, 121, 2931.

42

25) Morrill, C.; Grubbs, R. H. J. Org. Chem., 2003, 68, 6031. 26) Labadie, J. W.; Tueting, D.; Stille, J. K. J. Org. Chem., 1983, 48, 4634. 27) Matsubara, K.; Iura, T.; Maki, T.; Nagashima, H. J. Org. Chem., 2002, 67, 4985.

43

り

さ 1)

(1) (2)

(3) ↓

(4) Ⅴ

500 Υ1,3- ㌹ 2) さ

3)

sp2- - (Scheme 1)

Si-C p ┞ - (Vertical Stabilization) ┞ Si-C p

さ -

(Non-vertical Stabilization) Lambert4 )

Scheme 1

Si

Si ESi E

Si = SiR'3

E Nu

Si

vertical

stabilization

non-vertical

stabilization

or

ぜ

5)

さ TMSOTf TiCl4, AlCl3 Lewis6 )

44

(TBAF) ″ 7)

Lewis - -

syn-(E)- Z syn

(Scheme 2) 8) Scheme 2

(Z)-anti 8a)

レ

Scheme 2

H Me

H

SiMe3

Me3SiMeO

OMe

+cat. Me3SiOTf

O

tBu H

Me

OMe OMe

+

Me H

H

SiMe3

O

H tBu

from (E)-allylsilane

from (Z)-allylsilane

97 : 3

92 : 8

Me

Me3Si

MeO

OMe

Ph+

cat. Me3SiOTf

Ph Ph

OMe OMe

+

from (E)-allylsilane

from (Z)-allylsilane

75 : 25

28 : 72

TS

, -㌹ぜよ

anti-SE (Eq. 1) 9)

RE

RZ

Ph

SiH Si = SiR'3

E RE Ph

E HRZSi

Nu RE Ph

E RZ

(1)

ぜ ↓1c) Lewis

り Wender⒢ (–)-Laulimide

45

々ぜ

(Eq. 2) 10)

O

CHO

H

TBSO

OTBS

O

SiMe3

Me

HH

OiPr

OiPr

O

O

B

O

CF3

CF3

O

O CO2H

(1.0 eq.)

EtCN, –78 °C, 11 h

86% (>90%de)

O

O

Me

H

H

OTBS

TBSO

HO H

O

HO

O

H

O

O

O

H

HHO

HH

Me

(2)

(Scheme 3) 11) 3, 12) Wittig13) ふⅤ

1,3-り (Z)- 14)

1,3-

├

Doyle りレ

(Eqs. 3) 15)

㈻ Ⅴ

Scheme 3

M (X)R

Si-X (M)

R'

Ar3PSi

SiR

R

R Si

R

H-Si

cat.

H-Si

cat.– H2

cat.H-Si, cat,

RCHOAllylsilane

Rh2(pfb)4 or H2PtCl6R SiR'3

pfb = perfluorobutyrate

R'3SiH

R

(3)

46

-- (LnM-H)

- [NiHL4]+, RuHCl(PPh3)3, RhH(CO)(PPh3)3 り (Figure 1)

--

❻ (Figure 2) -

Figure 1. Isomerization via σ-Alkyl Complex

CH CHR

MLnH

CH CHR

MLnH

CH

MLn

CH2R

H2C CH CH2R

MLnH

H2C CH CH2R

H3C

H3C

H3C

Figure 2. Isomerization via π-Allyl Complex

CH CHR

MLn

CH CHR

MLn

H2C CH CH2R

MLn

H2C CH CH2R

CHH2C CHR

MLnH

H3C

H3C

り ┘16) ┘

り17a) り

18)

❻19)

り

ぜ㈻

り

(Eq. 4) 20) り

り

47

2Cl– OTf– SbF6

–

-Lewis Lewisり 21)

OH

SiMe3

( )n

cat. PtCl2-2AgX

(X= OTf, SbF6)

n = 1, 2

Si = SiMe2R

(4)

OH

SiMe3

( )n

OR1R1CHO ( )n

オ

り

(Scheme 4)

Scheme 4

R SiMe3

R1

OMe

R

Ph

Ph

R

cat. PtCl2-2AgX

(X = OTf, SbF6)

R SiMe3

R1CH(OMe)2

Ph2CHOR2

48

(Z)- 1a (2a) (Table 1) り (10 mol%)

3a (Entry 1) Eq. 42a

3a (Entry 2)

3a (Entry 4)

Table 1. Pt-Catalyzed Reaction Using Various Silver Salts

n-C10H21 SiMe3Ph

OMe

OMe

+

PtCl2 (10 mol%)

AgX (20 mol%)

Ph

OMe

n-C9H191a (2.0 equiv)

3a

CH2Cl2, 24 h

2a

Entry AgX Yield / % dr

1 none 0 –

2 AgOTf 78 63 : 37

3 AgOTs trace –

4 AgSbF6 60 73 : 27

5 AgBF4 8 70 : 30

6 AgPF6 28 72 : 28

(Entries 1–4 in Table 2) 70 Υ 3a よ

(Entry 2) 3a 々

(Entry 3) 40 Υ スよぜ (Entry 4) りさ

3a よ

(Entries 5–7) 40 Υ3a (Entry 6) 70 Υ 3a り

┘

(Entry 7)

49

Table 2. Optimization of Reaction Conditions

n-C10H21 SiMe3Ph

OMe

OMe

+

PtCl2 (10 mol%)

AgX (20 mol%)

Ph

OMe

n-C9H191a (Y equiv)

3a2a

(CH2Cl)2

Entry AgX Temp. / °C Time / h Yield / % dr

1 a AgOTf r.t. 24 78 63 : 37

2 AgOTf 70 1.5 72 61 : 39

3 AgOTf 70 24 Complex mixture.

4 AgOTf 40 12 71 64 : 36

5 a AgSbF6 r.t. 24 60 73 : 27

6 AgSbF6 40 10 89 74 : 26

7 b AgSbF6 70 4 84 63 : 37 aCH2Cl2 was used as solvent. bThe reaction was carried out with PtCl2 (5 mol%), AgSbF6 (10 mol%), and 1a (1.2 equiv).

1a

(Table 3)

4- 2c (Entries 1–5) 2c

々 (Entry 3) ├ 2f 々

2g (Entries 6 and 7)

Table 3. Pt-Catalyzed Reaction of Various Acetals

n-C10H21 SiMe3R

OMe

OMe

+

PtCl2 (X mol%)

AgSbF6 (2X mol%)

R

OMe


3

(CH2Cl)2, 70 °C

2

Entry R X Time / h Product Yield / % dr

1 Ph (2a) 5 4 3a 84 63 : 37

2 4-H3C-C6H4 (2b) 10 4 3b 74 69 : 31

3 4-MeO-C6H4 (2c) 5 2 – Complex Mixture

4 4-Cl-C6H4 (2d) 5 10 3d 83 71 : 29

5 4-O2N-C6H4 (2e) 5 24 3e 76 68 : 32

6 n-C8H19 (2f) 10 2 – <20 –

7 c-C6H 11 (2g) 5 2 3g 65 82 : 18

50

┘ 3a (Eq. 5) り

(Eq. 6)

(CH2Cl)270 °C, 2 h

n-C10H21 SiMe3Ph

O

H

+

PtCl2 (10 mol%)

AgSbF6 (20 mol%)

Ph

OMe

n-C9H191a (1.2 equiv)3a, 78% (dr = 60 : 40)

+ HC(OMe)3

(1.2 equiv)

(5)

Ph

OMe

OMePh

O

H

HC(OMe)3+Pt (II)

(6)

2a

(4a) り

1a (Table 4) 5 (Entry 1)

4b

6a (Entry 2) 4c 4d

┘ 6a (Entries 3 and 4) 7 5 6a

Table 4. Reaction of Diphenylmethanol and Its Derivatives

n-C10H21 SiMe3Ph

Ph

OR

+

PtCl2 (10 mol%)

AgOTf (20 mol%)

Ph

Ph


5

(CH2Cl)270 °C, 24 h

Ph

Ph

n-C9H19

Ph

Ph

n-C9H19

SiMe3+ +

6a 74a-d

Yield / %

Entry R 5 6a 7

1 H (4a) 48 0 0

2 SiMe3 (4b) 0 72 11

3 Me (4c) 0 79 7

4 Ac (4d) 0 88 3

(Table 5) 4e4f ┘ (Entries 2

and 3) (4g) tert- (4h) (Entries 4 and 5) 4d

51

Table 5. Allylation of Acetates

n-C10H21 SiMe3+

PtCl2 (10 mol%)

AgOTf (20 mol%)

1a (2.0 equiv)(CH2Cl)2

70 °C, 24 h

R

n-C9H19

64d-h

ROAc

Entry R Product Yield / %

1 Ph2CH (4d) 6a 88

2 PhMeCH (4e) 6b 15

3 PhCH2 (4f) 6c 3

4 H2C=CHCH2 (4g) – 0

5 t-Bu (4h) – 0

1a 4b (Table 6) 12 6a 7 8

(Entry 1) 24 8 6a 7 (Etnry 2) 48 6a, 7, 8 5

(Entry 3) Table 6. Reaction of Diphenylmethyl Silyl Ether

n-C10H21 SiMe3Ph

Ph

OSiMe3

+

1a (2.0 equiv) 4b

PtCl2 (10 mol%)

AgOTf (20 mol%)

(CH2Cl)2, 70 °C

Ph

Ph

n-C9H19

5

Ph

Ph

n-C9H19

Ph

Ph

n-C9H19

SiMe3+ +

6a 7

Ph

Ph

n-C9H19

SiMe3

8

+

Yield / %

Entry Time / h 5 6a 7 8

1 12 0 <65 <4 6

2 24 0 72 11 0

3 48 73 0 0 0

Table 6 4b (Scheme 5) り 4b

- 96a 7

8 7 8 6a6a り 5

52

Scheme 5.

Ph

Ph

OSi

Pt (II)

– SiOPt Ph

Ph

+ SiRPt (II)

R Si

Ph

R H H

Si

Ph

Ph

Ph

R5

Ph

Ph

R

Ph

Ph

R

Si +

6a7

Ph

Ph

R

Si

8

– H – Si

H

– Si

Si = SiMe3Si = SiMe3

R = n-C9H19

9

り

2 り

53

Ⅴ

Glass Tube Oven GTO-250 RS Ⅴ (bath temp.) (IR) FT/IR-230 ゝ

(1H NMR, 13C NMR) JEOL JNM-EX270 (1H NMR, 0.00 ppm) (1H NMR (CHCl3), 7.26 ppm) (13C NMR,

77.0 ppm ( )) (1H NMR (C6HD5), 7.16 ppm; 13C NMR, 128.0 ppm ()) ㈻ QP-5050

GC-17A ( DB-1 30.0 m0.25 µl 0.25 mmID 100 kPa 32.5 cm / sec 15

1.40 mL / min 2.5 mL / min N2)

モ

(CH2Cl2) (DCE) ⇩

モ

⇩

⇩ モ

モオ

1-( )-4- (2b): [3395-83-3]22)

OMe

OMe

Me

2b 4- 23)

(LiBF4, 14.1 mg, 0.15 mmol) 4- (0.60 g, 5.0 mmol) (2.5 mL) (0.68 mL, 6.5 mmol) 40 Υ 3

(10 mL) (10 mL 3)

54

⇩

(110 Υ / 2.6 Torr) 2b 93% 1H NMR (C6D6) δ 2.10 (s, 3H), 3.16 (s, 6H), 5.36 (s, 1H), 7.17 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H) ; 13C NMR (C6D6) δ 21.1 (CH3), 51.9 (CH3 2), 102.9 (CH), 127.2 (CH 2), 129.0 (CH 2), 136.1 (C), 137.9 (C) ; MS m/z (relative intensity) 166 (M+, 3.8), 135 (M+ – MeO, 100). 1-( )-4- (2c): [2186-92-7]22)

OMe

OMe

MeO

2c 4- 2b 1H NMR (C6D6) δ 3.16 (s, 6H), 3.28 (s, 3H), 5.38 (s, 1H), 6.81 (dt, J = 8.5, 2.0 Hz, 2H), 7.51 (dt, J = 8.5, 2.0 Hz, 2H) ; 13C NMR (C6D6) δ 51.8 (CH3 2), 54.7 (CH3), 102.8 (CH), 113.8 (CH 2), 128.5 (CH 2), 131.1 (C), 160.2 (C) ; MS m/z (relative intensity) 182 (M+, 6.1), 151 (M+ – MeO, 100). 1- -4-( ) (2d): [3395-81-1]22)

OMe

OMe

Cl

2d 4- 2b 1H NMR (CDCl3) δ 3.31 (s, 6H), 5.38 (s, 1H), 7.32–7.41 (m, 4H); 13C NMR (CDCl3) δ 52.5 (CH3 2), 102.2 (CH), 128.1 (CH 2), 128.3 (CH 2), 134.2 (C), 136.6 (C) ; MS m/z (relative intensity) 188 (M++2, 1.2), 186 (M+, 4.6), 155 (100). 1-( )-4- (2e): [881-67-4]22)

OMe

OMe

O2N 2e 4- 2b 1H NMR

(CDCl3) δ 3.34 (s, 6H), 5.48 (s, 1H), 7.64 (d, J = 8.8Hz, 2H), 8.23(d, J = 8.8Hz, 2H); 13C NMR (CDCl3) δ 52.6 (CH3 2), 101.5 (CH), 123.3 (CH 2), 127.8 (CH 2), 145.0 (C), 147.9 (C) ; MS m/z (relative intensity) 197 (M+, 0.44), 166 (M+ – MeO, 100). 1,1- (2f): [18824-63-0]24)

n-C8H17

OMe

OMe

2f 2b 1H NMR (C6D6) δ 0.90 (t, J = 6.4 Hz, 3H), 1.25–1.41 (m, 12H), 1.66 (td, J = 6.8, 5.6 Hz, 2H), 3.18 (s, 6H), 4.35 (t, J = 5.6 Hz, 1H); 13C NMR (CDCl3) δ 14.3 (CH3), 23.1 (CH2), 25.1 (CH2), 29.5 (CH2), 29.9 (CH2), 30.0 (CH2), 32.3 (CH2), 32.9 (CH2), 52.0 (CH3 2), 104.6 (CH); MS m/z (relative intensity) 156 (M+ – MeOH, 2.3), 71 (100).

55

(2g): [18231-08-8]25) OMe

OMe

2g 2b 1H

NMR (C6D6) δ 0.96–1.24 (m, 5H), 1.57–1.72 (m, 4H), 1.89–1.94 (m, 2H), 3.16 (s, 6H), 3.94 (d, J = 7.2 Hz, 1H); 13C NMR (CDCl3) δ 26.2 (CH2 2), 26.8 (CH2), 28.4 (CH2 2), 40.3 (CH), 53.0 (CH3 2), 108.5 (CH); MS m/z (relative intensity) 127 (M+ – MeO, 6.4), 75 (100).

( ) (4b): [14629-59-5]26)

Ph

Ph

OSiMe3

4b 27)

(1.84 g, 10.0 mmol) (25.4 mg, 0.1 mmol) (40 mL) (HMDS, 1.67 mL, 8.0 mmol)

(10 mL) 5 5

(125 Υ / 0.81 Torr) ( ) (4b, 2.44g, 9.5 mmol) 95% 1H NMR (CDCl3) δ

0.07 (s, 9H), 5.75 (s, 1H), 7.18–7.35 (m, 10H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 76.5 (CH), 126.5 (CH 4), 127.0 (CH 2), 128.2 (CH 4), 144.8 (C 2) ; MS m/z (relative intensity) 256 (M+, 31), 167 (M+ – OSiMe3, 100), 73 (100).

(4c): [1016-09-7]28)

Ph

Ph

OMe 4c 29) ◢ (III) 9

(162 mg, 0.40 mmol) (3.68 g, 20 mmol) (0.89 mL, 22 mmol) 80 Υ 1

(110 Υ / 0.58 Torr) (4c, 1.41 g. 7.1 mmol) 36% 1H NMR (CDCl3) δ 3.38 (s, 3H), 5.24 (s, 1H), 7.21–7.37 (m,

10H); 13C NMR (CDCl3) δ 57.0 (CH3), 85.4 (CH), 126.9 (CH 4), 127.4 (CH 2), 128.4 (CH 4), 142.0 (C2) ; MS m/z (relative intensity) 198 (M+, 88), 167 (M+ – OMe, 100).

(4d): [954-67-6]30)

Ph

Ph

OAc 4d

(3.68 g, 20.0 mmol) (7.27 mL, 90.0 mmol) (7.27 mL, 76.9 mmol) 18

(100 mL) TBME (50 mL 3) (50 mL2) 1N (50 mL) (50 mL) (50 mL)

⇩ (128 Υ /

56

0.62 Torr) (4d, 4.40 g, 19.4 mmol) 97% 1H NMR (CDCl3) δ 2.17 (s, 3H), 6.88 (s, 1H), 7.25–7.38 (m, 10H); 13C NMR (CDCl3) δ 21.2 (CH3), 76.9 (CH), 127.0 (CH 2), 127.8 (CH 2), 128.4 (CH 4), 140.1 (C 2), 169.9 (C) ; MS m/z (relative intensity) 226 (M+, 16), 165 (100).

(1- ) (4e): [93-92-5]31)

Ph

Me

OAc 4e 1- 4b 1H NMR

(CDCl3) δ 1.54 (d, J = 6.6 Hz, 3H), 2.07 (s, 3H), 5.88 (q, J = 6.6 Hz, 1H), 7.24–7.36 (m, 5H); 13C NMR (CDCl3) δ 21.3 (CH3), 22.2 (CH3), 72.3 (CH), 126.1 (CH 2), 127.8 (CH), 128.5 (CH 2), 141.6 (C), 170.3 (C).

Schlenck (0.025 mmol)

(0.050 mmol) 1,2- (1.5 mL) (0.50 mmol)

(0.60 mmol) 70 Υ ス

り

┘ 3-[ ( ) ]-1- (3a)

Ph

OMe

n-C9H19 Bp 149 Υ (bath temp., 1.2 Torr). 1H NMR (CDCl3) for the major isomer δ 0.87 (t, J = 6.3 Hz, 3H),

1.19–1.32 (m, 16H), 2.29–2.38 (m, 1H), 3.21 (s, 3H), 4.01 (d, J = 6.4 Hz, 1H), 4.84 (dd, J = 17.1, 1.8 Hz, 1H), 4.92 (dd, J = 10.2, 2.0 Hz, 1H), 5.47 (ddd, J = 17.1, 10.2, 9.2 Hz, 1H), 7.21–7.36 (m, 5H); for the minor isomer δ 3.19 (s, 3H), 4.02 (d, J = 6.4 Hz, 1H), 4.94 (dd, J = 17.1, 2.0 Hz, 1H), 5.06 (dd, J = 10.3, 2.0 Hz, 1H), 5.63 (ddd, J = 17.1, 10.3, 9.1 Hz, 1H); 13C NMR (CDCl3) for the major isomer δ 14.1 (CH3), 22.7 (CH2), 27.0 (CH2), 29.3 (CH2), 29.6 (CH2 2), 29.7 (CH2), 30.0 (CH2), 31.9 (CH2), 50.9 (CH), 57.0 (CH3), 87.2 (CH), 116.2 (CH2), 127.3 (CH), 127.6 (CH 2), 127.9 (CH 2), 139.0 (CH), 140.4 (C); for the minor isomer δ 51.0 (CH), 127.4 (CH), 127.5 (CH 2), 128.0 (CH 2), 139.5 (CH), 140.6 (C); MS m/z (relative intensity) 256 (M+ – MeOH, 0.38), 121 (100). 3-[ (4- ) ]-1- (3b)

Me

OMe

n-C9H19

Bp 161 Υ (bath temp., 1.9 Torr). 1H NMR (CDCl3) for the major isomer δ 0.87 (t, J = 6.7 Hz, 3H), 1.13–1.33 (m, 16H), 2.29–2.37 (m, 1H), 2.35 (s, 3H), 3.17 (s, 3H), 3.97 (d, J = 6.6 Hz, 1H), 4.95 (dd, J =

57

17.1, 2.1 Hz, 1H), 5.06 (dd, J = 10.4, 2.0 Hz, 1H), 5.63 (ddd, J = 17.1, 10.4, 9.1 Hz, 1H), 7.11–7.16 (m, 4H); for the minor isomer δ 2.34 (s, 3H), 3.19 (s, 3H), 4.85 (dd, J = 17.2, 2.1 Hz, 1H), 4.92 (dd, J = 10.4, 2.1 Hz, 1H), 5.47 (ddd, J = 17.2, 10.4 9.4 Hz, 1H). 3-[(4- ) ]-1- (3d)

Cl

OMe

n-C9H19

Bp 152 Υ (bath temp., 1.1 Torr). IR (neat) 1491, 1466, 1092 cm-1; 1H NMR (CDCl3) for the major isomer δ 0.87 (t, J = 6.7 Hz, 3H), 1.16–1.34 (m, 16H), 2.21–2.34 (m, 1H), 3.19 (s, 3H), 3.97 (d, J = 6.3 Hz, 1H), 4.83 (dd, J = 17.1, 2.0 Hz, 1H), 4.93 (dd, J = 10.4, 2.1 Hz, 1H), 5.43 (ddd, J = 17.1, 10.4, 9.2 Hz, 1H), 7.15 (d, J = 8.4 Hz, 2H), 7.26–7.32 (m, 2H); for the minor isomer δ 3.18 (s, 3H), 4.01 (d, J = 6.1 Hz, 1H), 4.91 (dd, J = 17.1, 2.0 Hz, 1H), 5.05 (dd, J = 10.4, 1.8 Hz, 1H), 5.59 (ddd, J = 17.1, 10.4, 9.1 Hz, 1H), 7.18(d, J = 8.2 Hz, 2H); 13C NMR (CDCl3) for the major isomer δ 14.1 (CH3), 22.7 (CH2), 27.1 (CH2), 29.3 (CH2), 29.5 (CH2), 29.7 (CH2 2), 30.0 (CH2), 31.9 (CH2), 50.9 (CH), 57.0 (CH3), 86.5 (CH), 116.6 (CH2), 128.1 (CH2), 128.9 (CH 2), 133.0 (C), 138.5 (CH), 138.9 (C); for the minor isomer δ 51.1 (CH), 116.5 (CH2), 128.2 (CH 2), 138.9 (CH), 139.2 (C); MS m/z (relative intensity) 290 (M+ – MeOH, 1.7), 155 (100). 3-[ (4- ) ]-1- (3e)

O2N

OMe

n-C9H19

Bp 195 Υ (bath temp., 0.95 Torr). IR (neat) 1523, 1346, 1105 cm-1; 1H NMR (CDCl3) for the major

isomer δ 0.87 (t, J = 6.9 Hz, 3H), 1.20–1.35 (m, 16H), 2.26–2.37 (m, 1H), 3.23 (s, 3H), 4.10 (d, J = 6.6 Hz, 1H), 4.81 (dd, J = 17.1, 1.8 Hz, 1H), 4.94 (dd, J = 10.0, 1.8 Hz, 1H), 5.43 (dt, J = 17.1, 10.0 Hz, 1H), 7.40 (d, J = 8.8 Hz, 2H), 8.19 (d, J = 8.8 Hz, 2H); for the minor isomer δ 4.84 (dd, J = 17.3, 2.0 Hz, 1H), 5.04 (dd, J = 10.3, 1.5 Hz, 1H), 5.57 (dt, J = 17.3, 10.3 Hz, 1H), 7.41(d, J = 8.9 Hz, 2H), 8.20 (d, J = 8.9 Hz, 2H); 13C NMR (CDCl3) for the major isomer δ 14.1 (CH3), 22.7 (CH2), 27.0 (CH2), 29.3 (CH2), 29.55 (CH2 2), 29.58 (CH2), 29.9 (CH2), 31.9 (CH2), 51.0 (CH), 57.4 (CH3), 86.4 (CH), 117.2 (CH2), 123.2 (CH 2), 128.2 (CH2), 138.0 (CH), 147.3 (C), 148.5 (C); for the minor isomer δ 51.1 (CH), 57.5 (CH3), 86.2 (CH), 123.2 (CH2), 128.1 (CH 2), 137.9 (CH), 148.6 (C); MS m/z (relative intensity) 301 (M+ – MeOH, 0.38), 166 (100). Anal. Calcd for C20H31NO3: C, 72.04; H, 9.37; N, 4.20. Found: C, 72.18; H, 9.60; N, 4.38. 3-[( )( ) ]-1- (3g)

OMe

n-C9H19 Bp 147 Υ (bath temp., 2.9 Torr). 1H NMR (CDCl3) for the major isomer δ 0.88 (t, J = 6.6 Hz, 3H),

0.96–1.80 (m, 27H), 2.14–2.22 (m, 1H), 2.72 (dd, J = 6.3, 5.3 Hz, 1H), 3.42 (s, 3H), 4.98 (dd, J = 16.8, 2.0 Hz, 1H), 5.01 (dd, J = 10.4, 2.2 Hz, 1H), 5.60 (ddd, J = 16.8, 10.4, 9.5 Hz, 1H); for the minor isomer δ 4.96 (dd, J = 17.6, 2.3 Hz, 1H), 5.04 (dd, J = 10.5, 2.1 Hz, 1H), 5.69 (ddd, J = 17.6, 10.5, 9.6 Hz, 1H); 13C NMR (CDCl3) for the major isomer δ 14.1 (CH3), 22.7 (CH2), 26.3 (CH2), 26.6 (CH2 2), 27.3 (CH2), 27.4 (CH2), 29.27 (CH2), 29.34 (CH2), 29.63 (CH2), 29.66 (CH2), 29.8 (CH2), 30.8 (CH2), 31.9 (CH2), 40.9 (CH), 47.2

58

(CH), 61.6 (CH3), 90.0 (CH), 115.2 (CH2), 141.0 (CH); for the minor isomer δ 41.2 (CH), 46.7 (CH), 89.5 (CH), 115.7 (CH2), 139.3 (CH); MS m/z (relative intensity) 262 (M+ – MeOH, 0.65), 127 (88), 95 (100). 2- -1,1- -1- (5)

Ph

Ph

n-C9H19 Bp 188 Υ (bath temp., 1.1 Torr). 1H NMR (CDCl3) δ 0.88 (t, J = 6.7 Hz, 3H), 1.00 (t, J = 7.5 Hz, 3H),

1.11–1.41 (m, 14H), 2.10 (t, J = 7.8 Hz, 2H), 2.13 (q, J = 7.5 Hz, 2H), 7.12–7.30 (m, 10H); 13C NMR (CDCl3) δ 13.4 (CH3), 14.1 (CH3), 22.7 (CH2), 24.8 (CH2), 28.5 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2), 31.2 (CH2), 31.9 (CH2), 126.0 (CH 2), 127.90 (CH 2), 127.95 (CH 2), 129.25 (CH 2), 129.32 (CH 2), 137.5 (C), 140.9 (C), 143.50 (C), 143.58 (C); MS m/z (relative intensity) 334 (M+, 24), 91 (100). 3-( )-1- (6a)

Ph

Ph

n-C9H19 Bp 206 Υ (bath temp., 1.2 Torr). IR (neat) 1495, 1452, 910 cm-1; 1H NMR (CDCl3) δ 0.87 (t, J = 6.7 Hz,

3H), 1.21–1.39 (m, 16H), 2.81–2.92 (m, 1H), 3.72 (d, J = 10.6 Hz, 1H), 4.87 (dd, J = 16.8, 1.8 Hz, 1H), 4.90 (dd, J = 10.6, 1.8 Hz, 1H), 5.44 (ddd, J = 16.8, 10.6, 9.1 Hz, 1H) 7.03–7.31 (m, 10H); 13C NMR (CDCl3) δ 14.1 (CH3), 22.7 (CH2), 27.0 (CH2), 29.3 (CH2), 29.5 (CH2), 29.6 (CH2 2), 31.9 (CH2), 32.8 (CH2), 47.9 (CH), 57.3 (CH), 116.0 (CH2), 125.9 (CH), 126.1 (CH), 128.1 (CH 4), 128.45 (CH 2), 128.53 (CH 2), 141.2 (C 2),.144.1 (CH); MS m/z (relative intensity) 334 (M+, 0.51), 167 (100).

59

1) (a) Brook, M. A. Silicon in Organic, Organomtallic, and Polymer Chemistry; Wiley: New York, 2000.

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