Russian Chemical Reviews, 2014, # 9, pp 885-895

http://dx.doi.org/10.1070/RC2014v083n10ABEH004471?locatt=label:RUSSIAN

:

..,a, b * ..,a ..,a ..,c, d * .fi.,c

..,c .'.,e * ..fi,e .fl.fl,e ..,a * ..,a

..,f, d * ..,f, d ..,f, d ..,g * ..,c

..,c, d ..fl,e, h * ..,e .fi.fi,e fi..fl,e, i *

..,i ..fi,i ..,i .fl.,h * ..,h fi..,h

fi..',h ..,e, j * .., j .fl., j ..,k, l *

..,k, l ..,a * ..,a ..fi,a ..,m*

..fi,m ..,c ..,a * .. a

a . fl..' , 119991 fi, ., 47b - , 199034 -, ., 7 9c . .. , 630090 fl, . , 5d fl , 630090 fl, . , 2e fi . fi.., , 119991 fi, , 1, . 3f fi , 630090 fl, . , 3g , 644040 , . fl, 54h . .fl.fl , 119991 fi, . , 28i . .. , 119991 fi, ., 29j . fl.. , 117393 fi, . , 70k , 620990 , . , 91l .fl., 620002 , . fi, 19m - , 659322 . , . , 1

83 (10) 885 985 (2014) # 2014 , . fl..'

I.

- .1 -

- - (sustainable che-mistry) (e-factor) (cost-

* :- fl .. (V.P.Ananikov),e-mail: [email protected];- fl .. (V.I.Bukhtiyarov),e-mail: [email protected]; , .'. (S.Z.Vatsadze),e-mail: [email protected]; .. (A.D.Dilman),e-mail: [email protected]; , .. (I.V.Koptyug),e-mail: [email protected];- fl .. (V.A.Likholobov),e-mail: [email protected]; , ..fl(V.G.Nenajdenko), e-mail: [email protected];

I. 886II. 889III. K 895IV. - 899V. K - 905VI. N- 909VII. . 915

VIII. 924

IX. 928

X. 935XI. 942XII. 949XIII. 955XIV. 961XV. 966XVI. ' 972

. . , , . - (atomic precision) . , . , , , - -, - -, , , , , , , . 840 .

fi..fl (M.S.Nechaev),e-mail: [email protected]; .fl. (S.N.Osipov),e-mail: [email protected];- fl .. (S.A.Ponomarenko),e-mail: [email protected];- fl .. (A.A.Rempel),e-mail: [email protected]; .. (A.Yu.Stakheev),e-mail: [email protected]; , ..(S.V.Sysolyatin), e-mail: [email protected]; .. (A.O.Terentev),e-mail: [email protected]

30 2014 .

V.P.Ananikov et al.886 Russ. Chem. Rev. 83 (10) 885 985 (2014) [ 83 (10) 885 985 (2014)]

efciency).2 6 - - ( -), ( ), - ( ) - .7 12 - , .. , - -. - .13 18

, - , , - ( -, , -, , - ).

. , , (H2O2, O2) (H2). , (, ) , , .

XXI . - . fl - ( - , -

) (- , - ). .

7 -7, , , , - , . - - , , - . - - . - - - , - 7.

, - (

fl , - , ( - (ppm) (ppb)). , -, .20, 21

- - , . -, - -. , , , , , . , - , - .

- , . - , - .

7 - . - -.

II , , - . , , - - ( II.1). ` ( III), - ( III.1).

fl 7 - ( IV) - - ( V). - C7O ( IV.1) C7P ( V.1). - .

, -

(metal/ligand structural units), . - 7-, 7. fl N-- ( VI). - -,, , ,, , , ( VI.1, VI.2).

, : , ( VII), . - - VII.1, VI.

, 7- 7, - - ( ). - -, - ( VIII).

- - . . (, , -). - - ( IX); - ( IX.1) - ( IX.2).

- ( X), -, ( X.1, X.2). fi - - ( XI, XII) ( XIII).

- - ( II XII). - (molecular building blocks) - .


- ( XIV). - ( XV).

, - . , ( , 42008C), - .

II.

, , - . ,, - -. , .22, 23

fl XX . ( ), - - ( ). fl - . 80- . , - .24

.25, 26 , , - .27 30fl - 31 34 - . 2.

, , -. -, , , - . fl *20% , -, . 30%.35

, , .36, 37 , -.

, - -

. , -, - , , . , .

- ( - !). C7F, , - , .38

- C7F - .

XX , .22, 39 10 15 , .40 44 - II.1 , , - . , - . , - , ,, , , - .45, 46

II.1. CF3- CF2 CF

. , , -.

O

F

F

HO

H

H

O

SO

F

O

()

()

(- )

N

O

N

NMe

F

O

OH

O

O

SO

NN

CF3

H2N

. 2. - -.

V.P.Ananikov et al.Russ. Chem. Rev. 83 (10) 885 985 (2014) [ 83 (10) 885 985 (2014)] 889

, , , , . - , , - . III.

II.1.. fi CF3-

- .47 - - - (, F3CLi, F3CMgBr) - (7788). CF3- () (1) ( - ). ' (--, -, -) 1 - , - ( 1).

1

1 47 49 50 ( C=N) 51 CF3- - ( 2). ( , - ; - .) - - - .52

2

fl fi - . - ( 3).53 55 a,b-, , . 2 - . (L) 2 , -

3, 1 - .56, 57

3

fi - - , - .41 - RPd(L)CF3 . 2010 . - ( 4).58 - - - .59

4

, (I).41 1 (.60) (-) , - in situ - (I)

Me3SiCF3

1

X7

Si Me

X

CF3

Me

Me

7

CF37

X7=F7, AcO7, ButO7

R

OH

CF3

Me3SiCF3, X7

R

O(1)

R1

HN

CF3R1

N1, X7

R2 R2

R

Z2

Z1Me3SiCF3, AcO7

Z1=Z2=CN; Z1=NO2, Z2=CO2Me; Z17Z2=

O

O

O

O

R

Z2

CF3

Z1(1)

R1 OR3

R1

O

O

R2

OR3

O

2

(DHQD)2-PHAL (10 15%)CF3 O

(ee 78 98%)

(DHQD)2-PHAL=

N

H

N

OMe

ONNN

H

N

MeO

O

R1 OR3

O7

O

R2

OR3

O

L+3

2

CF3 O

L R1

Me3SiCF3,

(1)O7

O

R2

= L

Cl, 1308C

CF3

Et3SiCF3, KF,cat Pd, L

PdCl

2

cat Pd = ; L =Pri Pri

Pri

MeO

OMe

PBut2

R R


( 5).61 , 1,10- (phen) CF3Cu(phen) - . , - , , - .62 .63

5

- . fl - SN1 SN2. 2006 . 4 5 - ( 6).64, 65

4, 5

. C- (1,3-- , a-, -), , ,, . fl 6 - 5 - fi.66

6

fl - CF3- . , . -, - 5 - ( 7).67, 68 , PdII/PdIV, CH- .69

CF3- - (6) (. 7).

7

fl 2010 . - , - - ( 8). fl, 1 KF CF3- - 7, .70 , , - , (. 8).71

8

.42

, , -. , ( 9). p- (, ), CF3-. CF3- -

CHF3

CuCF3

R CF3CuCF3

(Y = Cl, Br, OC(O)CF3)

ButOK, CuCl, phen

ButOK, CuCl, Et3N .HF

Me3SiCF3

1

R X

Br YYI

R X= , , ,

CF3

I OF3C

I OF3C

O

4 5

+

(ee>93%)

R

O

R

O

CF3

CuCl (5%), CHCl3,7208C

5,N

NH

O

Bn

Me

(20%)

.CF3CO2H

Ar CF3Ar B(OH)25, CuI (5%), phen (10%)

K2CO3, 358C, 14

BF4R

N

CF3

S

CF3

N

Pd(OAc)2 (10%),

Cu(OAc)2 (1 .)

1108C, 48

(6)

+

R

R CF3R +Me3SiCF31

CuI (20%), phen (20%)

KF, , DMF,1008C

7

R1

N

R3

R2

R1

CF3N

R3

R21, Cu(OH)2 (10%),phen (10%)

KF, AgNO3, ClCH2CH2Cl,

808C

.CF3

I O

F3C

OCF3 S

O

O

Cl,

CF3 S

O

OM

4

,

e

7e

CF3 I,

I O

F3C

5

.CF3

R R

CF3

H[O]

R

CF3

H7H+

R

CF3. +

9


. , , - .

, CF3- 2,2,2-- , ( 10). Pd- - - , - - Xanthphos SPhos.72, 73 2,2,2- 8, b--. (8, M=B(OR)2), -.74

10

II.1.. fi CF2-

fl CF2- ( ) ( 11).75 - ( ; 9). fl - 10 (.76) 11.77 - , , .

11

, - CF2-.78, 79 - (XCF2CO2H; X=Cl, Br) , - (CF2Br2, ClCHF2), fi- - .

, .44 , -

, - ( 12).80 . -, , , , . , - - C7C.81 - ()(12) -.

12

- , - 1,2-- ( 13).82 - ,, , - () 83 - .84, 85 , - , - .

13

1,1- 13 - ( 14). - 14 in situ 86 - 15, - .87

CF2- - - , (,88

89), -,90 91 92 (. 3). fl

Ar B(OR)2

F3C NuF3C INu

F

FFF

F

M

7MF8

Ar

CF3F3C I

cat Pd0, Xanthphos SPhos

R1

O

R2

: SF4 HF, R2NSF3 (9), R2N=SF2BF4 (10),

R1 R2

F F

But

Me

Me

SF3

(11)

+

R ZnBr

F F

Nu E

F F

Nu E

R ZnBr

I2, Br2, AcOH, AllBr; E = I, Br, H, All

AcO7F F

Me3Si

F F

Br

12

F FC

C

F FC

R E

F F

R

FF

R

R

FF

R

CF2:

O

OM

F F

X

(X = Cl, Br)

O

OY

F F

SF

O O

(Y = SiMe3, Me) (X = F, Cl, Br)

Me3Si

F F

X

, ,

F FC

F FC


7 (C7S, C7P, C7Si) , -.

II.1.. fi C7F

- ().93 - , ,- . - -, -, .94

' , - , - , . fl - 16, - , ( 15).95

15

' C7F, .96 '

- ( 16).97 (I) (I) -.98

16

- 7 ( 17). . - 7,99 . Selectuor NFSI - , - . - N- - ( M=Li, MgX). ( - ) - (, , ,) , , .

17

- - .fl 18 - 17, - 18., 19, N7F .100 , , 17, .

.fi.fl .101 104 , , -

N NAr Ar

F F

ROH

Ar = 2,6-Pri2C6H3

+CsF (3 .)

80 1108C, 3 20

RF

16

ROTf

RI

a

b

aCsF, cat. Pd0 R3P, 80 1308C, 14 ;b (ButCN)2CuOTf (3 .), AgF (2 .), DMF, 1408C, 22

RF

MR

"F+" FR

M= Li, MgX, B(OR)2, SnR3;

"F+" = XeF2,N

N

Cl

F2BF4

TfO7

NFSI

,+

+N

F

S S

O O

Ph

OO

Ph N

F

,

Selectfluor

+

O

O7Ph3P

F F

PPh3

F

F

PPh3

F

F

R

O(14)

14

13

15

Ph3P + CF2Br2

+

F

R F

14

Me3Si

F F

ZnBrNC

F F

SiMe3

P

F F

M

EtOEtO

A

F F

MPh

M= SiMe3, Li A = S, M= SiMe3;

M=K: A= Se, Te

M= SiMe3, MgX, Li

M= SiMe3, ZnX

S

F F

MAr

O O

F F

MRO

O

O

. 3. CF2-.


- , . . - ( - )( 19).101 , - - ( 2,3-, - ).

19

- ( *08C). , , -.101

. , - - ( 20). - - (300 5008C), (808C) (I) CuCl LiCl .103, 104

20

- a,b- -, .105, 106

(), - , -.36, 37 18F, 109.7 . -, 18F, . 18F - , . , 18F , (.. -). , , , .

X= Cl, F

FCHFX2

620 7008C 7HX

(75 85%)

F

X

CHF2Cl

(65 72%)

620 7008C

F

F

F

7HF

FF

R

F

FR

CHF2Cl

620 7008C

CHCl2F

KOH (.), BnNEt3Cl

Cl F

(82%)

F

Cl

MeCN, 808C

F

4508C

(76%)

+

(3 : 1)

CuCl (5%),LiCl (5%)

MeCN, 808C

CuClCHCl2F

KOH (.), BnNEt3Cl

Cl F

F

Cl

F

Cl

Me2N NMe2 ON

OAr

F

ONH

O Ar

(ee>87%)

18 (5%), Selectfluor (1.25 .)

7208C, 24

17 (1.1 .),

O

P

O

O

O7N

N

Cl

F

*

+

+ O

P

O

O

7O

*

19

Pri

Pri

O

OP

H17C8

H17C8

Pri

Pri

18= =O

OHP

O OH

* O O

18

7OTf

18F

I

I

I I20

a

+

20

b

18F

B(OH)220

18F B(OH)2

Icat Pd, pH 8, 378C, 30

(20)

18F

aH18F, K2CO3, K-222, DMF, 1458C;bB2(OH)4, cat Pd, AcOK, DMSO, 908C

21


- ( ) . fl 21 ,107 , , 20, 18F. 20 , - - K-222 ( , - ).

, CF3-, , - - - . fl - SN2- .

CF2-. fl, - (CF2X, X=Cl, Br, I) , - .

III. K

. - - , . - - .

- - . , fl 2005 ., , , .108 113

-, - , , , (Ring Closing Metathesis, RCM), - (Cross Metathesis, CM), - (Ring Opening Metathesis Polymeriza-tion, ROMP), (Acyclic Diene Metathesis, ADMET), -- .114 117 - (. 4) - - , .

- , .111 ,

a- , - .118

, , - -.22, 32, 119 a- -. , , , - , -.120 - - , , `fi 19F. , a--, b-, - - , .121

, - a- - - .

III.1. aa-

III.1.. fi

1,7-, a-, - 122 1996 . (n=1, 22). , - G-I (. . 4): - a- 1,6- (n=0,. 22) a,b-- . -, - (n=13, . 22).123, 124

a-

G-II

H-II

G-I

N NMesMes

Ru

Cl

Cl Ph

PCy3

PCy3

N NMesMes

O

Cl

Cl

RuRuCl Ph

Cl

PCy3

Cy , Mes=2,4,6-Me3C6H2

. 4. -: I (G-I) II (G-II) , - II (H-II).


1998 .125 , - - - - . - 5 .% G-I, - . a- (n=0, m=1, 23).126

23

2- 4,5-, - 4, - (ROM-RCM).127 -1,7-, - , - N- - . -1,7- G-I , - -, , -, - ( 24).

24

, , , : - A B, [2+2]- C. - D, , , - , - - ( 25).

25

III.1.. fi

(Ring-Closing EnyneMetathesis, RCEYM), , - -, - .128, 129 - - , C7C 1,3- , .

1,3- a-- RCEYM - . , - . , - - .130

1,6- 1,7-, - a-XCF2-a-. , - 131 , - [2,3]-

N

XF2C

MeO2C

PG

X=F, Cl; PG=Cbz, Boc, SO2Ph (Cbz , -); n=0 2; m=1, 2;aRMgBr (R , , ), THF,7788C;bRBr (R , ), DMF, 08C;c G-I G-II (3 5 .%), CH2Cl2, 208C

(56 75%)

a, b n

m

XF2C CO2Me

NPG

N

MeO2C

XF2C

PG

(85 97%)

n

m

c

[Ru], rtN

F3C

MeO2C

PG

F3C CO2Me

NPG

n1)

2) AllBr, NaH

(77 85%)

PG=Cbz, Boc, SO2Ph; n=1, 2; rt

n

N

F3C

MeO2C

PG (74 86%)

n

N

F3C

MeO2C

PG

n

DN

F3C

MeO2CRu

n

PG

C

N

F3C

MeO2C

Ru

n

PG

Ru

Ph

PG

MeO2C

F3C

N

Ph

A

N

F3C

MeO2C

PG

Ru

Ph

n

n

B

N

F3C

MeO2C

PG

Ru

[Ru]

N

R1

R2O2C

PG

N

R2O2C

H

PG

N

R2O2C

R1

PG

(R1 = H)

(n=0)

(n=173)

n

n

PG ; [Ru]=G-I, G-II,H-II

22


CF3- ( 26).132

26

, -1,6- 5 8 .% [Ru=C=C=CPh2(Cl)(PCy3)(p-cymene)]+TfO7, - [RuCl(PCy3)(p-cymene)]+TfO7 HC:CCPh2OH. 2,3--4,5- (DDQ), - ( 27).131

27

, -1,7- -

(G-II) (H-II). - -- 1,3- ( 28).133

, - 1,1-- , ,117 -1,7-, RCEYM 1,1- , ---. Pd- - -1,7-, , . , -1,7- - , - 1,3- ( 29).133

29

- - a-, - [4+2]- 1,3- N- ( 30).

30

, - 1,6- 1,7-. , , 5 .% Cp*Ru(cod)Cl(Cp*=Z5-C5Me5; cod -1,5-), - c ( 31). -

R MgBrXF2C CO2Me

NPG

N

XF2C

MeO2C

PG

R

(42 78%)

1)

2) AllBr, NaH

F3C CO2Me

N2

N

MeO2C

F3C Me

N

Cu(F3-acac)2 (5 .%),PhMe, D

7+

Me [2,3]

Me

F3C

MeO2C

N

(76%)

F3-acac 1,1,1-

[Ru]

N

XF2C

MeO2C

PG

R

PhMe, 808C

N

XF2C

MeO2C

PG

R

CO2Et

CO2Et

(40 70%) (40 52%)

N

PG

MeO2C

XF2C

R

EtO2C CO2Et

DDQ, PhMe, 1108C

X=F, Cl; PG=Cbz, Boc, SO2Ph; R=H, Bun, CH2OMe;

[Ru]= [Ru=C=C=CPh2(Cl)(PCy3)(p-cymene)]+TfO7

R = Ar, Aroyl, Acyl; [Ru] = G-I, G-II,H-II; B

N

MeO2C

F3C

MeN

MeO2C

F3C

Me

R

(70 95%)

PdCl2(PPh3)2,

CuI, B[Ru]

RCEYM

Me

F3C

MeO2C

N

R(67 75%)

R= Ph ( 78%), 4-MeC6H4 (74%)

N

MeO2C

F3C

Me

R

NO O

Ph

PhMe, 1108C

N

MeO2C

F3C

Me

NO

O

H

HH

Ph

R

+

(3 : 2)

N

MeO2C

F3C

Me

NO

O

H

HH

Ph

R

Me

F3C

MeO2C

N Me

F3C

MeO2C

NN

CO2Me

CF3

Me

Me

F3C

MeO2C

N

G-II H-II

PhMe, 708C

+

(20%) (40%)

28


Z--, -.134

31

- - E, - H (E?F?G?H), . , H - ( ), - - . , , (TMS) F - . ,

TMS- ( 32).

III.1.. fi . 1,2,3,4--3-

- - , - , - - . , , - , - .135 - a-, .

, , - , , , . 1,2,3,4--3-- (TIC), , - , d- - -.136, 137 fl TIC- (Accupril1),138 (. 5). TIC-, , -, .

CF3-TIC- 139 ,140 - -1,7- (G-II). - -1,7- CF3(X)C=N7PG (X=CO2Me, P(O)(OEt)2)) 141 -

PG

F3C

MeO2C

N

N2CHCO2Et

N2CHSiMe3

Cp*Ru(cod)Cl (5 .%),Et2O, rt

Cp*Ru(cod)Cl (5 .%),, 908C

PG=Boc, Cbz, Ts; n=0, 1

PG

F3C

MeO2C

N SiMe3

H

(53 75%)

n

(60 80%)

PG

F3C

MeO2C

N

H

CO2Et

n

n

N

O

N

Ph

O

EtO

HO2C

Accupril1

H

R4N

R3

R1(O)C

R2

,

R4N

R3

(R1O)2(O)P

R2

2013 .

. 5. 1,2,3,4--3-- .

[Ru(Cl)Cp*]

N2CHSiMe3

H

PG

F3C

MeO2C

N Ru

SiMe3

Cl

n

G

F3C

MeO2C

NRu

SiMe3

ClPG

n

E

Cp*(Cl)RuSiMe3

F

PG

F3C

MeO2C

N

Ru

Cl

H

SiMe3

n

PG

F3C

MeO2C

Nn

PG

F3C

MeO2C

N SiMe3

H

n

32


: 1) -; 2) Pd- - ; 3) N- ( 33).

33

Ru- - -1,7- (-, -1-, -1- ), (DCE) 5 .% (G-II) - - - ( 34). - 92%, 2-MeO-- >97%.

34

- - -1,7- I, - . - - J?K?L, - -. - [2+2]- Ru=C J, K, - - ( 35).

, a-- , - , -

, .

, - , - - -. - - , - , ( RCM) ( RCEYM) . , - - Z- - - . Z- E- E-.142 - . - ,143, 144 ,145, 146 - .147, 148 - ,149, 150 , - .

IV. -

- C7F, -- . ,

N

F3C X

PG

F3C

NHX

PG

(53 79%)(65 82%)

a b, cF3C

X

N

PG

Ar

X=CO2Me, P(O)(OEt)2; PG=Boc, Cbz, Ts;

Ar=Ph, 2-MeC6H4, 4-MeC6H4, 4-MeOC6H4, 4-O2NC6H4;

aHC:CCH2Br, Mg, HgCl2, Et2O,7788C;bArI, PdCl2(PPh3)27CuI (5 .%), , rt;cNaH, HC:CCH2Br, DMF, 08C

N

F3C

X

PG

Ar

R

R

F3C

X

N

PG

Ar

+DCE, 508C, 3

+

(62 82%)

RuPhCl

N NMes Mes

PCy3

Cl

PG=Boc, Cbz, Ts; Ar=H, Ph, 2-MeC6H4, 4-MeC6H4, 2-MeOC6H4,

4-O2NC6H4; X=CO2Me, P(O)(OEt)2; R=H, Ph, Bun, n-C6H13

N

F3C

X

PG

Ar

R

J

R

N

F3C

X

Ar

Ru

Ph

PG

PhL

N

F3C

X

Ar

Ph

PG Ru

R

Ph

Ru

K

N

F3C

X

Ar

PG

RuR

I

NPG

F3C

XAr

Ru

Ph

- -

NPG

F3C

XAr

N

F3C

X

Ar

PG R

=Ru

Ph+ PCy3

RuPhCl

N NMes Mes

Cl

35


7 - . - C7O, -- ( V) N- - ( VI).

- (oxi-dative cross-coupling, cross-dehydrogenative coupling, CDCreaction) - . , , . - - , - (Hal,OTf, BR2 , SiR3 , SnR3 , ZnHal). , - - .151 154 - .

- , - . - , , -.

- - C7C-, C7O-.151 154 - C7O-- - - O- . C7O O-,O- O-. OH- (O-) , , , . - C7O O- , O- , (--) 155 156 - .O-, , , ; - , .

IV.1.

fl O- C7O-- , , . C-- , (, , -, , ), , - C7H- ( ,

, ). - , - (, -), .

- CH- 36.157 , C7H , - CuII (I) CuIII, C7O - . fl - ( ), .

36

Pd(OAc)2 , K2S2O8 , (,KHSO5 . 0.5KHSO4 . 0.5K2SO4), PhI(OAc)2; - , , N--, . fl, - Pd(OAc)27MeSO3H7K2S2O8( 37, ).158 -, -

R1

N

(32 82%)

R2OH, Cu(OAc)2,

AgOTf, O2

1408C, 24

R1

N

OR2

BunO

Ph

N

(57%)

BunOH, Cu(OAc)2,

AgOTf, O2

1408C, 24

R2=Et, Bun, Pri, CH2All, CH2Bn, (CH2)2OMe .

R1

N

CuIII

R2O X

fl-

Ph

N

NH

O

fl-

(36 77%)

NH

O

OR

ROH (510 .), Pd(OAc)2,K2S2O8, MeSO3H

MeO(CH2)2OMe, 258C, 24

R=n-Alk, cyclo-Alk, (CH2)2Cl, (CH2)2OMe

37


C7Pd7OR, - C7O-. O- , - .

- . - N-(-8-) (III), ( 38).159 , - , - ; 91%. fl .

38

CH- O- Pd(OAc)27PhI(OAc)2 AcOH7Ac2O ( 39).160 CH- . -

CH3- '- .

. , - p- -; (, ) . fl - ( 40).161

Z- .

40

C7O- Bun4NI7ButOOH ( 41).162 , , - - -. ; - .162, 163

41

Bun4NI7ButOOH C7O- - ( 42).164 , 20- . -, Bun4NI7ButOOH - a-- ; -

fl

OI

O

X

ROH ROH7

N

N

O

H

Pd(OAc)2 (cat.)

N

N

OOR

H

X=OMe, OAc

Pd(MeCN)4(BF4)2 (10 .%),DMSO (1.4 .), Pri2NEt (70 .%),-1,4- (2 .)

MS (4A), CH2Cl2, , 418C, 72 HO

O

+

(3 .)(1 .)

O

O

(53 75%,

E :Z 5 : 1 >20 : 1)

+

(4 .)

a

OH

O

(1 .)O

O

aBun4NI (20 .%), ButOOH (70%- .) (1.5 .),PhH, 808C, 8

Y

O

O

Y=2-MeC6H4 (89%), cyclo-C3H5 (79%),

CH2Bn (80%), CH2NHBoc (67%)

O

O

Cl

ZZ=Bn (23%), thNaph (85%),

CH2C(Me)=CPh2 (98%),CH2CH=C6H10-cyclo (72%)(thNaph 1,2,3,4--1-)

NHO

AcOH7Ac2O (1 : 1)

258C, 2

NAcO

OAcNAcO

(33786%)

Pd(OAc)2 (5 .%),PhI(OAc)2 (13 .)

80 1008C, 4 12 (one pot)

fl-

Br

NOAc

OAcH

NOAc

N

O

O OAc

N

OAcN

OAc

OAc

(61%)(65%)

(41%)(86%)

( )

5

OAcH

39


, .

42

C- . fl, - C7O- N-- Bun4NHal7ButOOH (Hal= I Br, 43);165 - , . - . - I2 , (III), N-- .

43

Bun4NI7ButOOH ButOOH ( 44). - - .166 , - - ( 45). , - - TEMPO (2,2,6,6--N-) (. 44).

C-, C7O-, . - Pd(OAc)27CF3SO3H7DMA7O2 (DMA ) -, - ; ( 46).167 , -, C7H

PdII. PdII, (. 46). , Pd0 PdII

Pd0, - C7H - PdII (.167).

46

MnO2 DDQ. , DDQ , - . - DDQ.

R OH

OO+

(1 .) (20 .)

R=Ar, Het, PhCH=CH, BnCH2, n-C15H31;aBun4NI (20 .%), ButOOH (70%- .) (2.2 .),EtOAc, 808C, 12

a

O

OR

O(66 98%)

R1

O

+

(2 .)

R1

O

O

O

OR2

NR3

(43 98%)

R3N

R2OH

O

O

(1 .)

a

OH

F3C

F3CR4

O+

(1 .) (2 .)

bR1

O

O

CF3

CF3(79 93%)

R1=Ar, Het, 4-ClC6H4CH=CH, PhCH=CBr, But;R27R3=CH2CH2, -; R4=Ar, PhCH=CBr;aBun4NI (10 .%) Bu

n4NBr (10 .%),

ButOOH (5.5 M - ) (2 .); EtOAc, 708C, 7 12 ;bBun4NI (10 .%), ButOOH (5.5 M - ) (2 .),EtOAc, 708C, 6

R O

O Ph

R OH

O

+

(0.5 ) (64 92%)(0.5 )

Pd(OAc)2 (10 .%),CF3SO3H (10 .%),DMA (0.5 ),O2 (1 )

1158C, 24

C7O

R=Ar, PhCH=CH, 4-FC6H4CH2, n-C7H15, cyclo-C3H5, Cy

R O

O Ph

+ Pd0

R OH

O

PdII

PdIIRCOO

ButOOHR

O

OO

ButR

O

H

Bun4NI (20 .%)

(0.5 ) (43 92%)

+

(1.5 )

H2O (2 ), 408C, 24

R=Ar, Cy

N

.O

H

O

+

Bun4NI (20 .%),ButOOH (3 .)

H2O (2 ), 408C, 24

O

O

N

(99%)

44

I7

ButOOH

0.5 I2

ButO.+HO7

ButOOH+HO7H2O+ButOO.

R

O

OO

But

ButOO.

R

OButO.

R

O

H.

45


fl C-- (O--) .168 2,3--5,6--1,4- C7O- , -, , 168 O- C- ArCH=CHCH2R ArC:CCH2R .

Cu(OAc)27ButOOH - C7O- - ( 47).169 C7O C7H; - Bun4NI7ButOOH, , .170

47

C7O- - N- CuCl7PhI(OAc)2 (.171) (NH4)2Ce(NO3)6 ( 48).172 CuCl7PhI(OAc)2 (NH4)2Ce(NO3)6 , .-, C7O - -N- , - , . N-- .171

48

C7O- a-

. - (III), in situ -, - . : - -, O- C7O- ( 49).

49

, -() - b- OH-: , , ( 50).173

50

C7O- - Bun4NI7ButOOH ( 51).174

- , - , C- O--

R1

O

O

R3

R2

R3

R1

O

+

(1 )

(60 88%)

(2 )

Cu(OAc)2 . 2H2O (0.1 ),ButOOH (2 )

1008C, 1.5 7

R2

R1=Ar, 2-Th, PhCH=CH, Cy; R2=Me, Cl; R3=H, Me;Th

N

O

O

HO+a b

O

O

O

N

aCuCl7PhI(OAc)2, 708C, 12 ;b (NH4)2Ce(NO3)6, 20 258C, 30

ROH

O O

IX

7XH,74-MeC6H4I(X = OR, OH)

..

..

O O

OR

I

X

OR

OH O....

IF2

O O

+

(20 258C)

O O

OSO2R

O O

OAc

O O

OAlk

O O

OP(O)(OPh)2

a b

c

d

aRSO3H (R=Me, 4-MeC6H4), 5 30 ; b (PhO)2P(O)OH,15 20 ; cAcOH, 15 80 ; dAlkOH (Alk =Me, Et, Pri),0.5 24

R1

O

R2

O R3

O

R3COOHR1

O

R2+

(1 .)

(1 .)

Bun4NI (10 .%),ButOOH (2 .)

EtOAc, 50 758C,4 53

(61 99%)

R1=H, Ar, Het, Me, OMe; R2=Alk, Ph, Bn, Ac, CO2Alk .;R3=Me, Ar,

51


1 : 1. , . , .174

N- N- - C7O- 1,3- - , 2- - , , .175 fl - Mn(OAc)3 Co(OAc)2 (.)7KMnO4 , 94% - ( 52). fi -N- - . , -- : N- N- N- 1,3- -.

52

fl 1,3- , ,, ( 53).176

KMnO4 ,Mn(OAc)27KMnO4 , Mn(OAc)3 . 2H2O, MnO2 , Mn(acac)3

(acac ), Fe(ClO4)3 , Cu(ClO4)2 . 6H2O,Cu(NO3)2 . 2.5H2O, (NH4)2Ce(NO3)6 . KMnO4 , Mn(OAc)3 . 2H2O Mn(OAc)27KMnO4 20 27 92%. . in situ .

, - 1,3- 177 178 -, - (Cu, Fe, Co, Mn).- O- , Cu(ClO4)2 . 6H2O( 54).

54

fl C7O-- - , ( 55).179

55

- -, - .

, - - . fl C7O-- , C7O7R O- .

C7O- - , C- O--. . , , - .

C7O- , ; , , -

EWG1 EWG2

O

O N

N

O

O

H

EWG2EWG1

H

(30 94%)

Mn(OAc)3 Co(OAc)2 (cat),

KMnO4

AcOH, 60 808C,10

EWG1, EWG2= CO2Et, Ac, CN

C7O

O

O

O N

OO O

M(n+1)+

7Mn+

NO

.O

EWG2EWG1

H

ButOOH,Cu(ClO4)2 . 6 H2O (cat)

MeCN, 79 1198C, 0.25 2

EWG2EWG1

ButOO

EWG1, EWG2=CO2Et, Ac, CN(37 94%)

R1 O

O

R3

R2N

N P

But

But

HO

R2

R3R1 OH+

(46 99%)(1 .)(2.5 .)

(1 .%)

PhMe, D, 24 38 ,72H2

Ru

CO

H

AcOH, 40 608C,10

Mn(OAc)3, Mn(OAc)27KMnO4, KMnO4

(27 92%)

H

OO

NO

HO

OO

N

C7O

7Mn+

O O

M(n+1)+

O

O

N

O

N

.O

53


; C- O- ; - .

V. K -

, - -, . , - - . - , 100%- (-),4, 180 . - , - .

- C7B, C7O, C7N, C7Si,C7P, C7Se, C7Sn, C7Te .181 183

, - .

fl 7 184 186 - 7 (, , , ).

, (Z E) .187, 188

, , - . , C7P, (Pd, Ni, Rh .) . - (

, (PPh2Me PPhMe2) (. 56).201 - - .

, Ph2P(O)OH Ni- PV7H- Ph(EtO)P(O)H Ph2P(O)H.201 , , - . , 201 - (Ph2P(O)H) , , Ph2P(O)OH. - PV7H-. , Ph2P(O)H .

[Ni]7Ph2P(O)OH PV7H- (H-, H-- Ph2P(O)H), -1,3- ( 57, 58).202

57

58

(. 56 58) 201, 202 . , 201

-1- - (. 56), 1 .% - , 2--3--2- (. 58) - 5 .%.

, 16 2 -1-. , - 5 8 - . , 10 .% Ph2P(O)OH (. 58) - 2 .% (. 56),

: 68 91% . -, 10 .% Ph2P(O)OH - : a- 77%, 2 .% Ph2P(O)OH 92% (. 56 58).201, 202 - - [Ni]7PPhMe27Ph2P(O)OH - .

fi - , Ni(acac)2 2010 .203 . - H- - - ( 59).

59

-- .204 - : 7 7. , M7H , M7P. 204 - - .

- H- .205 fl NiBr2 (10 .%) ( 60).

60

fl - , .. - . (, Ni(acac)2) - , , - -

[P]

R

ROH

(57 99%)

[P]7H+[Ni]7Ph2P(O)OH

7H2O (one-pot)

[P]7H=(MeO)2P(O)H, Ph2P(O)H, Ph(EtO)P(O)H;R=Me, Ph, 4-MeC6H4, 4-MeOC6H4, 4-Me2NC6H4 .

OH

+ (MeO)2P(O)H

Ni(PPhMe2)4 (5 .%),Ph2P(O)OH (10 .%)

THF, 208C, 16 ,7H2O

P(O)(OMe)2P(O)(OMe)2

(68%, a : b=77 : 23)

+

+ (R3O)2P(O)HR1 R2

Ni(acac)2 (9 .%),dppe (18 .%)

THF, 100 1408C,20 30 (R3O)2(O)P

R1 R2

(61 99%)

R1=R2=Ph, Et; R2=H: R1=n-C5H11, NC(CH2)3, Ph;

R3=Pri, n-C12H25, Bn, Ph; R37R3=CH(Me)CH(Me);dppe=Ph2P(CH2)2PPh2

R =Me, Et, Pri

Ph + (RO)2P(O)HN

Ts

Bn

NiBr2 (10 .%)

PhMe

N

P(O)(OR)2

PhTs

Bn (35 97%)


- (, Pd2(dba)3, dba -).206

fl Ni(acac)27DIBAL(DIBAL=Bui2AlH) - .207 - , . Ni(acac)27DIBAL Ni(acac)2 (1 9 .%): - 1,2- - ( 61).

61

fl , - .194, 198, 208 194, 208 198 - H-((MeO)2P(O)H,194, 208 (cyclo-OCMe2CMe2OP)(O)H 198, 208 (EtO)2P(O)H) 208 a- b-, .

- -. , Ni(acac)27dppe, - -1-,203 -1,6-.209 , - - , - .

2013 . .209 - 207 Ni(acac)27DIBAL 21 - H- . ( 91%). H- .209

21

V.1.. R2P(O)H()

, - - 90- . . , - , .

H- , PV7H--. , , H-. , , - Ph2P(O)H, , - Ph2P(O)OH, , . - Ph2P(O)H -.201, 202, 210 215 (Pd, Rh, Ni,Cu). , . - .201, 202

, Rh Ph2P(O)H - (MW),213 - . , Rh, b-(E )- ( ) - - ( ). 213 2 3 Ph2P(O)H ( 62).

62

, , - .213 , - , - .

, - Rh, Ph2P(O)H , .216

+ (R3O)2P(O)HR1 R2

R3 = Pri, n-C12H25, Ph

R2R1

(R3O)2(O)P P(O)(OR3)2

R1 R2

P(O)(OR3)2

Ni(acac)27DIBAL

[Ni] (9 .%)

[Ni] (1 .%)

(99%)

(99 %)

R1 = R2 = Ph, Et;R1 = Ph, R2 =Me

R1 = R2 = H, Ph;R2 = H: R1 = n-C5H11, Ph

P

PP

OR

ORORO

ORO

ORRO

O

R= Et, Pri, Ph

21

PRO

ROO

R1

P(O)Ph2Ph2(O)P

R2

R1 R2

R

P(O)Ph2Ph2(O)PR

40

20

Ph2P(O)H

(2 3 .)

[Rh]

,MW


(b-E-) - ( 63). PV7H ; , .

63

- Pd(PPh3)4,217 - Pd7M- (M=Ti, Zr, Hf); (408, 1 ) (>95%).218

215 Pd Rh 1r--2,5t-- . a- b-E- Pd- Rh-- ( 64). -, `fi 95%, - 25 40%,, 215, .

64

- : a- Ph2P(O)H, Pd.219 dppe a- (64 88%) (95 99%). (P(o-Tol)2Ph) (o-Tol -) , - (48%) .

2007 . CuI71,2-( 65).220 Ph2P(O)H Bn2P(O)H - PV7H- b- -.220

65

2011 . , - .221, 222 22 - PV7H- (H-, H- ) -.221 a- ( 66).

66

R1 R2 L T, 8C , , % a : b

n-C6H13 Ph dppp 70 3 99 98 : 2n-C6H13 Me dppp 110 5 99 98 : 2But MeO dppe 110 25 95 98 : 2But .a dppe 70 19 97 99 : 1

a R27R2=O(CMe2)2O; dppp=Ph2P(CH2)3PPh2.

CpPd(Z3-All)7dppben7[3,5-(CF3)2C6H3]2P(O)OH (Cp=Z5-C5H5, dppben=1,2-(PPh2)2C6H4) .222

V.1.. (RO)P(O)H2 H- (RO)(R0)P(O)H ()

, , . - ([Pd]7) .223 227 - NiCl2 - - .228 -, NiCl2 , Pd, a- b-.

Ph2P(O)H+MW

[Rh], H2O

OH

O

[Rh] = (Me2PhP)3RhMe3

OH

O

P(O)Ph2

(79%)

Ph

Ph

P

R

R

Ph

Ph

P

P

O

H

Ph

Ph

a (>95%)

(R,R)

+ R

b (57 >95%)

[Pd]

[Rh]

O

O

PhMe, 808C,15

[Pd]=Pd(PPh3)4, [Rh]= [Rh(cod)Cl]2

n-H13C6 + R2P(O)HCuI (10 .%)

H2N(CH2)2NH2 (15 .%),DMSO, 908C, 12 18

n-H13C6

P

O

R

R

(R=Ph, 67%; E :Z=85 : 15;R=Bn, 72%; E :Z>99)

R1 + R22P(O)H

(5 .%)7L

PhMe

R1

P(O)R22R22(O)P

R1

a b

+

PO

Pd(22)

Ph O


2007 . .229 (HOP(O)H2) --H- ( 67). fl -, - .

67

H- PV7H- -H--.201, 202, 220, 221, 230 , - a- Pd- .231 - Pd(OAc)27dppe ( 68).231

68

2013 . Montchamp .232 , Pd- 7. Pd(OAc)27dppf (dppf 1,10-()-) H- -4-.

, PV7H- - - C7PV-. (PV7H-, ) - (, , -). C7PV- - .

fl (. ), . -: 1) - - MW- ;2) ; 3) , , - ; 4) , ; 5) -, , , .

VI. N-

- . . N- (NHC) .

20 - , . 1991 . 23 Arduengo . 233 , . - . 234, 235 .236 240 -.241 244 fl - C7C C7N, (. III) - .245 250

23

- (24) -2- (25), - . - .' 10 , , - ( 26 28) (29, 30).251 - - - (31a), - (31b) (31c). N-- (expandedring NHC, er-NHC).252

R1 R2PHOH

H

+Pd2(dba)37Xantphos

DMF, N2, 858C

R2

R1

P

O

H

OOH

Ph + (EtO)PhP(O)H

Pd(OAc)2 (5 .%),dppe (7.5 .%)

PhMe, 1008C, 3

Ph

P(O)Ph(OEt)(EtO)Ph(O)P

Ph

+

a (89%) b 23

N N..

N

N

25

N

26

N

N

27

+7.. .. .. ..

.. .. ..

N

N

N

28

+

7

N

N

29

N

N

24

..

N

N

30

+

7

N

N

31a c

n= 1 (a), 2 (b),3 (c)

n

24 31


, , - :

;

; 7; ' -

, . -

- .

VI.1.

N- , - , Lappert 1977 .,253, 254 -. - C=C ( 69). - 2003 .,255 - (.256) 257

2008 2011 . .fi 258. - - , .

69

, 31a,256, 259 - ( ) - , ( 32, 33) 260, 261 (34) 255, 262, 263 . - (35) 264 (36),265 - (37) - (38).266, 267

32 38

- . , ( ) - ( 39);268

(40 41).269 - 42, -.270 fl , - (43),271, 272 (44),273 (45) (.274).

39 45

- . 46 .275 277 Bertrand .278 47, . -, , .

46, 47

, - , , . -, (31a),256 (48) 256 (49) 279, 280 , -

M=Cr, Mo

+ LnM(CO)

N

N N

N N

N

MLn

NN NN

O

NN NN

O

.. .. .. ..

32 33 34 35

NN

OO

NN

O7O

NN

OO

R

.. .. ..

36 37 38

45

N N

N N

39

N N

N

Ph

Ph

..

..

4140

N

NN

N

O

N

NN

N

O

..

..

. . ..

42

N

N

Fe

44

N N

PR2 PR243

N N

N NAr Ar

..

..

46

N

..N

47

N N..

48

NN

NN

O O

NNNN

49 50

NN

OO

51 52

....

..

.. ..

48 52


(50) 281 (51) 282 . - 52, .283 - 31, .257

N-- - . (. 69) - . fl - ( 70, a). ,255, 267, 278, 283 288 in situ -.259 261, 264, 265, 268, 269, 272, 275 277, 279 282 (. 70, b) - 288 290 (,291 - 280). , ' , - (. 70, c). - - .256, 257, 274, 277, 292 294 - C7H-- (. 70, d ) 273 CO2 - - (. 70, e).295, 296 2-- (. 70, f ),297 -, , g-- ( 70, g).298

70

fl , . , , ,. .253, 254, 272, 299 - - . .

-.271, 272, 274, 300 305 fl - -.255, 257, 260, 262 267, 272, 275, 281, 283 , . - .306

(, - .) . . ' 270, 275, 279, 280, 284 286 .268, 272, 275, 280, 283, 287

VI.2. K -, ,, ,, ,

VI.2..

- - ( 71). ' . .fl . fl- 2010 .307 fl - , , - 239 308 .309 - , , , .252

71

2006 . Herrmann .310 -

R N C M

N

N O7

O

H

N

N

H

N

N

H

N

N

AgHal

N

N

M

+

a

b

c

de

f

g

+

+

NH .HCl

R0N

N

n

n

n

n n

N

N

Hal

+

nn

+

M , [M] , B ,n=13; a [M]; b [M],7AgHal; cMB,7HB;d [M],7H2; e [M],7CO2; f [M]; g7HCl

Cl

..

R

X B(OH)2+

R0

[Pd]

R

R0

53 54

N

N N

N N

Bun Bun

N

N

Pd Cl

Pri

Pri

+ +PPh3

Cl

57 (Np )

N

N

Fe

Np

Np

..

58 (n= 0 2)

Ph

N

N

Ar

Ar

Pd

Cl

n

Y=Ar, X = Cl (55);Y = CH2OAlk,

X = Br (56)

55, 56

N

N

Y

Ar

X7

+

53 58


53 . , - , . - 0.005 .% -, 1 . 106 14 . 0.01 .% 6 . 103

.

in situ 54.311 ( 1.87 . 105,0.005 .% ), - .

,312 55 56 in situ , - - - 508C 2 , . , (1.5 3.0 .% ).

57.270 - - ., - - 1 . 1074 .%.

2013 . - 58 .288 , -,- (Mes, 2,6-Pri2C6H3 (Dipp)). fl - Dipp-. , , . . : ) -; ) , - ; ) , - NaHCO3; ) Bu

n4NBr;

) ; ) 1 ; ) - , . - - . . , - .313

VI.2..

- ( 72).314

72

2010 .295 - -, . - - ( 1 . 105). 59 3 .

59, 60

55 56 - - , - , , 2 >70%.312 2011 . , Pd0 , - ( 60), - -.286

50 100% 3 . (0.1 .%). , 57, - --.270

VI.2..

- .285 - NiI 61. 40 50% ( 73); - 30%.

73

VI.2..

Cavell .315, 316 62 63, - () . . 1 24 -

R0

R

R0R X+[Pd]

6059

PdCl Cl

NN

N N

PriPri

PriPri

SiO

Si

Pd

NNAr Ar

n

Ar=Mes, 2,6-Me2C6H3, 2-MeC6H4, 2-MeOC6H4; n=1, 2

HalR

R=H, Me, OMe, CF3; Hal=Cl, F; Ar=Ph, Mes;

Ar0=2,4,6-Me3C6H2, 2-MeOC6H4, 2-MeC6H4; X, Y=Cl, Br; n=13

(61)ArR

Ni

NNAr0 Ar0

Ph3P X

ArMgY,

n


, , . - -1-.293 , 1500 71, - , - -, - .

62, 63

VI.2..

2010 . , , .295 - . 0.1 .% 4 , - 88%, ee>82%)B2Pin2 ()

R OR

O

(1)

(5)R1

R2

OP(O)(OEt)270a (5.0 .%)Me2PhSi7BPin,

R1

R2

SiMe2Ph

N N

N

Ph

Ph

RCu

Cl

70a,b= (R=Me (a), But (b))

(25 88%, ee>78%)

M= SiMe3, BPin

BPinB2Pin2,70b (1 .%)

(>79%, ee>62%)

(2)OAr

(3)RO NO2

R

OH

70b (1 .%)2) H2O2

1) B2Pin2,OH OH

(>81%,

: >95 : 5)

(4)M

BPinM

O NO2B2Pin2,70b (1 .%)

(>75%, ee>98%)

75


. , - fi (. 75, (1)).268 - ( (2)) 322, 323 ( (3)) 324 *80%. - - ( (4)).325

2013 . 70a - Me2PhSi7BPin ( (5)).326

VI.2..

2004 . - 62 63 ( 76).327 , ( 99%). , . - X - , , - . , , . , , BF4 , , . .294 62 (. 76) - , 70 95%.328

76

VI.2..

300 62a d (R1=R2=Mes, n=1, X=Cl (a),OTf (b), OBut (c), OC(O)CF3 (d)), 66a,b 63(R1=R2=Mes, n=1: X=Cl, OC(O)CF3) - . (-, ) - ( 77). - - . 66a,b, , - 100%. 63 -.

77

- , -.295 ( : -=100 : 1) 2 -. 4.5%.

- , - ( 69), , ( 71a c).265 , - 69 , 71. - -, 62a d,66a,b, .

71

VI.2..

-. 2012 . Al Thag Lavoie 272 , (72 74 -), , () , .329 - , - , Cr 74. 72 73 .fl, 74 . , 74 3 4 , - , ().330

OH

+

62: X=Cl: R1=R2=Pri, Mes, CH2C6H2(OMe)3-3,4,5,CH2C6HMe4-2,3,4,5; X=Br: R1=R2=Pri, Mes;

63: X=Cl, Br; R1=R2=Pri, Mes

R2

B(OH)2

+62 63

NaOH, H2O

O

R1

R1 R2

O

R1 R2

Ph Ph Ph Ph

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Ph

7OTf

N N

Rh

O O

E

Mes Mes

E =Me (a), Tf (b), H (c)

71a c

+


72 74

VI.2..

331 , 75 - ( 78). >80% 3 6 .

78

fl - ( 79). - 76, -, - . -, , Dipp- . , - , . 2 .% 15 . .

79

. - - . , , -, . , ,, ,

. - - , , , - . fl, , -, -, , .

VII. .

fi , , - . - - .

. - , . .332 335

, , , , (. 6). -, (,

N N

MN

N

Cl Cl

M= Fe (72), Co (73)

72, 73

N N

CrN N

ClCl Cl

74

AuCl

Dipp

H2NR R0 +H2NNH2

(75)

N

R R0

Ar =Mes, Dipp; n= 0 2

MeOH, rt

NHR

N NAr Ar

Au

OTf (76)

n

N

R

N

COOH

HO

H

a

NH

b

N

COOH

H

N COOHH

flN

NH

N

H

N

N

OO

c

H

fi

N

O

Ph

O

N

N

Ph

O

Ph

HO

N

. 6. (a), (b) - (c), .


), . fl-, . , 200 - -. , , -, . 6.

, - a-. , , - , . - , - ( -) 10 15 .

VII.1.

- - N- 77 , . fl - 77 , - 78, - ( 80). , 79, , , 98%. , -, .336 338

80

79 N- 77 - - ( 81). 79. 79 80, 79 . , - 79, ,

- .339 342

81

o- 81 - 80, - 79. (Ni-Ra) ( 82).343, 344

82

- 82 83, 79( 83).345 347

83

- 79., o- 84 85, .348 - 79 ( 84).

84

N

PG

O

77

n

N

PG

O

R1

OR1COOR2, NaH

78

1) HCl, H2O, D

2) 7OH,7H2O

n

R1=CF3, C2F5, Alk, Ar, Het; PG=CH=CH2, CH(OEt)2; n=1, 2

NR1

n

79 (4 98%)

n

n

80

77

N

PG

O

1) RLi (RMgBr),

THF,7788C

2) H3O+R

NH3

O7OH

7H2O

79 (60 90%)

n

NR

+

n=1, 2

R= Alk, Ar, Het; n=1, 2

CNR

O 81

R

O

NH2H2, Ni-Ra

NH3 n80

7H2O

NR

79 (67 90%)

n

n

HalR1 R2

N

M

Ar

HalR1

CN

R2

82

ArM

83

NAr

R1R2

79 (478%)

R1=H, Alk; R2=H, Ar; n=1, 2

nn

n

R1

O

R2

N

R3

PPh3R1

O

R2

N3

R3

n

84

PPh3

n

85

R1=Alk, Ar; R2, R3=H, Alk; n=1, 2

NR1

R2

R3

79 (61 92%)


349 351 - , o-- 86 ( 85). - , , .

85

, 79 87 ( 86). fl 87 , , (ButOK, MeONa, ).352, 353

86

VII.2.

VII.2..

. - . , 2,5-1- 2,6- 79 . (PtO2),354 ,355 357 ,358 - .359 - - 88 . (-

,360, 361 362) -- 88 ( 87).

-2,6- 89 - . Et3Al - 89 (. 87).362, 363

3 --. , 2,3- 79 - 90 71% ( 88).364

88

-, -.fl, - 79b, 4, - - 91 ( 89).365

89

5--2- - 79c , , - 92 ( 90).366

90

- , - , .367

fl - .

(R)-1- (87a) 2- (79d) (96%) (ee 98%). - 93 2 . - ( 91).368

fl 94, a- - 87b 79e (83 94%) (ee 50 61%)( 92).369

NR

R

NH2

cat

R=Alk, Ar; n=1, 2; cat=PdCl2, CpTiCl3, CpZrCl3, NaAuCl4,CpLaCH(SiMe3)2

nn

8679 (495%)

n=1, 2

NR

n

H

87N

R

n

79 (51 86%)

NR

Hal

n

NPh

Ph

NaBH4, MeOH

AcOH (cat)

79a

NPh

Ph

H

90 (71%)

NaBH3CNN

Ph

F3CN

Ph

F3C

79b

H

91 (71%, ee 98%)

Ar

RN NH

Ar

R

79c

NaBH3CN

MeOH

92 (65 89%)R= Alk, CF3

NR1 R2

n

79

88: R1=P(O)(OEt)2, Het, Alk, Ar; R2=Alk, Ar, CO2Me; X=H, Ts;n=1, 289: R1, R2=Alk

NR1

X

89 (64 91%) (anti )

LiAlH4, Et3Al

THF,7788C(n= 2)

NR1 R2

X

88 (62 98%) (syn)

n[H]

R2

87


91

92

95. 79 - 95 ( 98%) ( ee 98%) ( 93).370

93

, -m--(-1,5-)(I) (S,S)-f-BINAPHANE(96), - 79 87 - ( 94).371

94

, 79 ( 95). 99%, - >99%.372 376

95

VII.2..

C--, - C7C. fl, , a-, . , - -.377 79f ( 96). - 97 (87%).

96

VII.2.. ( fi)

p- fi . fl 98 - 79.378 , , - . , -

NPh

79d

H2, BuLi (0.2%), 93 (0.1%)

PhMe, 808C

(R)

93= TiCl

Cl

NPh

87a (96%, ee 98%)

H

N ArN Ar*

79e

HCO2H, 94 (1 .%)

Et3N, MeOH

H

87b (83 94%,ee 50 61%)

(R)

RuN

Cl

N

Bn

Ts H

PhPh

94 =

NR

79

n

Pri

RuN

BAr

F

H2N

Ms95=R=Alk, Ar, Het;

H2, Boc2O

95, CH2Cl2N

R

Boc

*

(90 96%, ee 67 98%)

n

n

79

NR

H2, [Ir(cod)Cl]2 (1 .%), 96

EtOAc, CH2Cl2, 508C

R=Alk, Ar; 96 =P

Fe

n

87 (96 99%,ee 50 89%)

*

NR

H

P

HN

RNR

*

79

n

87 (499%, ee489%)

n

R=Alk, Ar, Het

N

1) KCN, AcOH, DMF

79f

2) Ac2O, HCO2H

O

OMe

OMe

NMeNCHO

CN

(87%)

...

97

R2

N

R198

R1=H, Me; R2=Me, MeO; RF=CF3, C2F5; n=1 3

NRF

+

79

n

R2

RF

NR1

NH

99 (47 87%)

n

1) BF3 .Et2O

2) K2CO3, H2O

97


. 99 ( 97).

79 100 ( 98). b-. - a- (101a) b- (101b) *1 : 1. CF3- a-. N- - b-, .379, 380 , p- - 79 -.

98

VII.2..

79 102. 2---2- a- (103)( 99).381, 382

99

79g - .383 104 ( 100).

100

fl -, 105

- ( 101). , 106, 79h, 107 .384

101

VII.2.. fi

fi - , p- , . , 79i HCl - 108 83% ( - 4 : 1, ), ( 102).385

102

386 - 79j 109 HBr, in situ. fi, - , ( 103).

387. 79k, HCl

N

R

NF3C

+n

10079

BF3 .Et2O

N

R

NF3C

H

n

101a

+

NF3CH

n

N

R

101b

n

NR

79

1) C2F5Li, BF3 .Et2O, THF

2) K2CO3, H2O

R= Alk, Ar, Het; n=13; Fu

n

N

C2F5

R

H

102 (43 65%)

O3, MeOH

(R=2-Fu, n=1)N

C2F5

CO2H

H

103 (84%)

NP(O)(OEt)2

Ph

79g

MeMgBr

BF3 .Et2ON

Ph

P(O)(OEt)2

104 (76%)

H

106

+

N

(7)-105

79h

N

But

BOTf

Fe

Fe

N

But

BN

+

TfO7

N

SO2CF3

Me

107 (96%, ee 94%)

2) B7N

MgBr1)

79i

HCl, MeOH

D

PhPh

O

OMe

ON

O

H...

108 (83%, dr= 4 : 1)

PhPh

O

O

MeO

NO

OHN

O


, - fi, , ( 104).

104

fi 388, 389 390

( 105). . 79l - , 110 .

VII.2..

, , , - (). fi : , -, , - . a- ( 106).

106

2- - 79 - a-.391, 392 111, - , a-- ( 107).

107

fi - 79, ( TMSN3 MeOH), 1,5- 112, , ( 108).393, 394 - , N--

NOBn

O

ButO2C

TBDPSO

79k

OBn

N

O

Ha

OBnN

O

H

(96%)

...

OHN

O

aHCl, MeOH, D; TBDPS=ButPh2Si

+

N

R2

R1

R3

H

R5 N C7N

R2

R1

R3

R4COOH,

R5NC+

R4COO7

+

R5 N

NR1

R2 R3

H

O R4

O

R4N

O

NR5

O R3

R2R1H

R1 = CF3, C2F5, Alk, Ar; n= 1 3

+ R2NC+ R3CO2HCH2Cl2 n

N R1NHR2

O

C(O)R3

111 (45 95%)

n

NR1

79

PhH, D

79j

Br OH

OMe

ON

OAc H

O

OAcN

109 (70%)

103

NH

OPhO2S

R1

R2

Zn(OTf)2

N

TBSO

PhO2S

R1

R2

79l 110 (54 75%)

N

OH

OAc

N

O

...

...

R1=H, OTIPS; R2=H, Me; TBS=ButMe2Si, TIPS=Pri3Si

105

n

NR1

79

N

NHNN

NR1

H

n

113 (87 97%)

+ R2NC

TMSN3,MeOH

NR1

N

R2

N

N

N

H112 (5 84%)

n

H2, Pd/C

(R2=Bn)

R1=CF3, C2F5, Alk, Ar, Het; R2=Bun, But, Bn, All .; n=13

108


1fl-5- 113, (. 108).

VII.2..

79 (()) , a-- 114 ( 109). , - .395

109

VII.2.. -

396 79m - FR901483 ( 110). - , 79m (TMSOTf), 115 - Cbz-- 116.

110

VII.2.. -

397 399 , a-- 79 - , 117 ( 111). , - .

111

- 3- 79n BF3 .Et2O. - 118 54% ( 112).383

112

- DEPMPO, -. - 119 2- 79h, 120 66% ( 113).400 - DEPMPO 121, .

113

VII.2.. C=N 79 - (- (mCPBA) (MMPP)), 122 123 .401 403 79(R2=Alk, R3=CO2Et) - 122 ( 114). - -. , , , - .

NR

n

79

CF3TMS, KHF2, THF

MeCN, DMFN R

CF3n

114 (44 79%)

H

R= Alk, Ar, Het; n= 13

N79m

TMS CO2Me

(115)

CbzCl, TMSOTf, CH2Cl2,

778? 08C

N

Cbz

CO2Me

...N

AcO

O

FR901483116 (42%)

NR1

n

79

R1=CF3, C2F5, Alk, Ar, Het; R2=Et, Pri; n=1 3

HP(O)(OR2)2

BF3 .Et2O N R1

P(O)(OR2)2n

117 (44 79%)

H

79nN

Ph

HP(O)(OEt)2

BF3 .Et2O

118 (54%)

N

Ph

P(O)(OEt)2

H

O

C8H17

P

O

EtO H

+

N

79h

119

BF3 .Et2O

H2O, Na2WO4 (cat)

EtOH, H2ON

O

EtO P O O7+

121 (45%)

N

O7

P(O)(OEt)2+

DEPMPO

NH

O

EtO P O

120 (66%)


114

404 79o 124 (76%). 124 125 ( 115).

115

VII.2..

(LDA) , . , - - 126. - N-() 127, .. . 2- (79h)

, - 128.405 , - 79p - 129 39% ( 116).

2- 79e - 130 . ( 117).

117

fl 406, 407. 131 3--1fl--[2,1-][1,4]-1,2,4- 132 5---2,3- 133 . 131 -

79N

R1R3

R2 mCPBA (MMPP)

R1 =Ph, Me; R2 = Alk; R3 = CO2Et

NR3

R2

O

R1

cis-122

+NR

3

R2

O

R1

trans-123

(55 98%, 122 : 123=(2.1 4.0) : 1)

N

TBDPSO

C8H17

O

N

TBDPSO

C8H17

mCPBA

79o 124 (76%)

...

N

TBDPSO

C8H17

O

125

BF4+

N Ph

O7

CF3

N Ph

79e

1) LDA

2) CF3CO2Et

N

Ph

C(O)CF3

N

C(O)CF3

Ph

130

H

7

N

Ph

NH

S

OF3C

N

S

N

OF3C

NH

R

F3C

O

NR

n

79

H

128 (78%)

126 (27 67%)

(R=Me,n= 1)

LDA

CF3CO2Et

79: R=Alk, Ar, Het; n=13

1) LDA

2) CF3CO2Et

79p 129 (39%)

+ NR

OF3C

n

127

n

116

N

O

O

HO

ArH (79 82%)

(133)O

O

OAr

O

N

O O

C(O)Ar

OHO

N

O O

C(O)Ar

OO

(132)N

O

O

N

O

HO

C(O)Ar

134 (96 97%)

N

O

NH

O

131

NH Me Me

O

118


. 132 - - 134 ( 118).

VII.2..

[4+2]- 79, d- 135.408 in situ 136 [3,3]- ( 119).

119

fl 137 (a--) - . ( 120). 2- 79h a- 137

b-138, `fi. 138 , 139. - 140, - 25% (. 120).409

- - , in situ 79q, 141 142a,b ( 121). [3+2]- 143 146 1 : 1 141 2 : 3 (142a). (142b), - , 147 79r 1 : 1 67%(. 121).410

- , in situ - 79q, N- (148). [3+2]- 149 ( 122).

122

, - - . . , - - ,

R1=H, Me, Ph; R2=Me, Bun

S

TMS

R1136

N

S

R2

TMS

R1

135 (56 82%)

C

C

TMS

R1

SN(79)

R2

NR SnBun3

79q

+N

O O

Me

Me

148

MeI, PhMe

1108C

R=Me, Ph

Me N

Bun

N

O

O

149 (19 40%)

(142a)

(R1=Bun)

(R1=Bun)

BunLi, THF,7788C NR1 SnBun3

79q

NH

R2

R3R1

NH

R3

R2R1

R3R2

+BunLi, THF,7788C

(141)

NH

Bun

+

BunLi, THF,7788C

(142b)

NBun 79r

147

HN

Bun

HN

Bun

+

146 145(68%, 2 : 3)

R1=H, Me, Bun, Ph;

143, 144: R2=Ph, SPh, SePh; R3=Ph, H (67%, 1 : 1)

143 144

121

N

O

PhPh

AcO

Cl

+

N

79h

137

Et2AlOEt

THF

138

N

NO

Ph

HN

O

Ph

O

+

139140

120


10 15 . , . , , , , - .411 416

VIII.

II VII - ( , - .). , - , ,.417 (- , , - ).

- - .418 420 , - , - , - , .421 424 , ,425, 426 .. - . . - - . -, .. , - . , - , - .427, 428

- , - , , , .421 423 , , , .424 - - , - , , -.428

fl -

30 ,428, 429 -.418 420, 430 439 , ,418 ,419, 420 - 435 .. - , .440 , , ,418 - 441, 442 442 ..

- - . -, - , . - -. , ., - (Eg) 2.5 3 . , .. , , - . , , - . - . fl , - . , - , - , , , - - , .

VIII.1. ,

() 443 446 , - - . .447 - -, (). - , -


(48C) 5 . .

- - .448, 449 - , , -, 15 . 1 (- ) 5 . , CdS , - .447 , CdS, , . fi CdS . 7.

- - (fi ) - () , -

Cd2+ - CdS.

CdS@TiO2 CdS TiO2 . fl TiO2 CdS. CdS@TiO2 , , , P6, - 450, 451. fl CdS , CdS B3 (- ) B4 ( ), - . - *5 .

CdS@TiO2 , , fi .420 fl . 8,a,b - CdS@TiO2 (Degussa P25) CdS@TiO2(Hombine N). , , -

. . , Degussa , Hombine. Degussa CdS , Hombine (10 15 ), .

CdS@TiO2 . . l>400 . , .. , TiO2 .

CdS@TiO2 (Degus-sa P25) CdS@TiO2(Hombine N) 0.34 . 71. CdS@TiO2 (Hombine N) - 0.1 . 71.

, CdS@TiO2 - . - , - , . , CdS , , . .

, . 9,, - 1.49 . 71, 4 3 , . - CdS: 6 6 , .

a

b

CdS

CdS

CdS

TiO2

TiO2

TiO2

[001]

[101]

[101]-TiO2

10

10

. 8. fi- CdS@TiO2 (TiO2 Degussa P25 (a) TiO2 Hombine N (b)), - 258C.420

0

2

4

6

8

160 320 480

w0=1.49 . 71

w0=0.46 . 71

AcH

,

,

. 9. [email protected]


, CdS , .. , CdS7TiO2 . fi , - , CdS TiO2 (. 10,a) (. 10,b), .. 458 TiO2@CdS. - , , , CdS - , , - . 458 CdS TiO2 -. fl - CdS , -: - 459, 460 CdS. Ti(OBun)4 CdS. () *8 . ' - 1308C 3 . , , , *10 . TiO2@CdS - (fi) , 500 *10 , . 10 . , - 200 300 .

(. 11), CdS7TiO2 : TiO2 (92 .%) CdS(8.%).fiTiO2 CdS, (,. . I41/amd ) (, . . Pbca) - 1 : 3 .

- , . - CdS

*510 . - TiO2@CdS. - , .. CdS, - - () CdS. CdS TiO2 TiO2 - CdS , - , TiO2(. 12) TiO2 . , -. - .

, ,458 -, Ti(OBun)4 -

CdSCdS

CdS

CdS

TiO2

TiO2

TiO2

TiO2TiO2

TiO2 TiO2

a b

. 10. fi TiO2@CdS, - .a CdS *3 ;b CdS 3 5 *3 .

20 30 40 50 2 y,

1

2

3

. 11. TiO2@CdS(1), CdS (2) TiO2 (3), CuKa1,2-.458

fl CdS (. . P6) *3 .

e7

hn

CdS

TiO2

Eg=2.4

Eg=3.2

H+/H2

h+

CdS

. 12. TiO2@CdS. CdS TiO2 . - CdS hn >2.4 .


CdS , TiO2@CdS. - CdS - CdS . CdS TiO2 - CdS - TiO2 . , - TiO2@CdS - , - .

, - - , . - , () -.

, , - , - , - . ' -, , -. , - . - - -. - - , - . , -, . .

, , , . ( , - , , - ) - ( , --, , ). - , .

- . ' ex situ, in situ, .

in situ

- () - , . - - , - , .

- - . - - - .

IX.

, (. II VIII). - - . , - . - - , . XXII .

- , - , , - , ( ) - . , , , - , (`fi , --), , . - .

, - , (Pd, Ag, Au, Pt), - ( 2 . 71). - ( , , 1 2 .%) .


- - , .

- (Surface Science), -- . - , - ( 10 ), , .

- , - . , :

1) - () ( );

2) ( , , - );

3) - ( - ).

in situ, .. . , (P5 1 ) (P4 1076 ), , , , () , - . , , -, - . , .

- . 1935 . 461 -

2fl4+0.52 2fl4

- ,

Ag/a-Al2O3-. fi - .462

2fl4+0.52 +fl32fl CH3CO2CH=CH2 , - . AcONa LiCl - PdCl2 CuCl2 110 1308C 1 3 fi.463 , , 100 2508C 0.5 1.0 fi.464 - , , - . 0.1 10 .%. , .465

IX.1.

, - .

IX.1.. fi

, - 70 90- . XX ., , - , - . - *1 - 1 2 , - (

--.466 468 - , , - , . - . , - - . .469, 470

fl , - - . , - ( , ) , , -, , - (fi, - ), (, , ) . , ( - fi) (, Al2O3 , NiAl(110) (.466)), - (), .468

, , - in situ (., ,471).

IX.2. K

IX.2..

fl ,472 477 - -.472 475 - - , CO2, . in situ, - ,471

, , --.478 fl . 13 - -, - (fi) ; (pressure gap) . , fi P(C2H4)=0.07 , 1 - 420K.

' O1s , - (O), O1s528.2 . , ; , - CO2 H2O. 1 '- . , , (. 14). -, , (O), .478

- O (. . 14). fl ( 123).

123

C2H4O

RIC2H4O

CH3CHO

CO2 + H2OO

RI

0

400

800

1200

100 200 300 400 500

,

fi

C2H4O,ppb

300K 370K 420K 470K

C2H4+O2 C2H4

1.05

0.0715

2

1

. 13. fi - :P(C2H4)=0.0065 , P(O2)=0.065 (1); P(C2H4)=0.1 ,P(O2)=0.95 (2).478

- O2.


, - - , .479

IX.2..

, - , , - >50 .480 , O1s- Ag/a-Al2O3 , , - (O , . ). - , - , - , fi fi - . -, in situ. - , -, - , 1078 2 . 71 (.481), . .

- - . , .468 fl . 15 fifi- Ag/ - Ag :C& 0.5, - - (.) (. . 15,a)

(. . 15,b) - 2508C. , , - , , - - . Ag/(Ar) - -: . fi (. . 15,c,d ). Ag/ - Ag , : 1) ; 2) ( , - ); 3) T5 2508C - .

fi. fl . 16 - fi- Ag/(Ar) - ( O2 : C2H4=5 : 1, P=0.25 ) . , 2308C (. . 16,a), 2508C - (. . 16,b). - Ag/- in situ

12

0

0.0004

0.0008

0.0012

0.0016

0.002 0.004 0.006 0.008 0.010 0.012

O1s :Ag3d5/2

C2H4O,

. 14. (1) - (2) .478

dz=11.9 dz=6.5

a b

c d

fl

. 15. , fi (5006500 )(a, b) fi (c, d ) Ag/ (.) (a, c) Ag/(Ar) (b, d ) 2508C 1 (dz ).468


2308C, ,, , - .478

- Ag/(Ar) 8 40 . fl . 17 fi- , -

Ag/ (8 ) Ag/ (40 ), 170 2108C.482 fl, , -,480 , Ag/ (. . 17,c,d ). -. 1s - 529.2 , .482 E(O1s)=530.3 O , - (. . 17,a,b). - .482 , - - , .480

, -, , , , ,

a b

. 16. fi- Ag/(Ar), - - (P=0.25 ) 230 (a) 2508C (b).468

a b

530.8 529.2

530.8531.9

532.8533.9

531.9532.8

533.9

2108C

1908C

1708C

1508C

2108C

1908C

1708C

1508C

526 528 530 532 534 536 538 526 528 530 532 534 536 538

, ,

0

2

4

6

8

10

160 170 180 190 200 210 160 170 180 190 200 210

,.

, 8C , 8C

0 50 100 150 200 250 0 50 100 150 200 250

c d

, ,

. 17. O1s- (a, b) - (c, d ) Ag/ 8 (a, c) 40 (b, d ).482

: C2H4 :O2=2 : 1, P=0.5 .


Ag+

(.479). p- C7H. - , ,477 -.480 - , - Ag7Cu-- , - .483

IX.2..

p- - , .fl , ( 124).

124

C2H4+3O2 2CO2+2H2O

CH3CO2H+2O2 2CO2+2H2O

CH3CO2CH=CH2+2.5O2 2CO2+3H2O

484. , - (413K) 485 , . CO2 , 3.5 CH3CO2CH=CH2 , 5%.484 fl , , , , .

-- () Pd/SiO2 Au7Pd/SiO2.486 , - , -, . SiO2 , Mo(110), -.487 fl SiO2 1 (fi), - ( 0.1 1 fi), 800K. - , 90K - T=250K. ( 215K) (. 18,a).

D2 , C2D4(. . 18,b), C2D4 p-. , D2 , - - (. . 18,b), - -s-, - .486 - , .

- (Ion Scattering Spectroscopy, ISS),488 --.489 , - Mo(110). - (1400K) (1420K),486 -

180 200 260 300 240 T, K

fi-

m/z30

250 K

230 K

215 K

310 K

470 K

1

3

5

a

fi-

m/z4

250 350 450 550 T, K

b

1

2

3

4

5

. 18. 2D4 (a) D2 (b), 2D4 ( 2.0 ) 90K - ( (): 1 =1076 . ).486

1 Pd(1 fi)/SiO2, 2 Au(0.1 fi)/Pd(1 fi)/SiO2, 3 Au(0.2 fi)/Pd(1 fi)/SiO2, 4 Au(0.4 fi)/Pd(1 fi)/SiO2, 5Au(1 fi)/Pd(1 fi)/SiO2.


. - fi 490 - , - ISS -. - , , () () - .486, 490

: 1) Pd/Au/Mo(110) 2) Au/Pd/Mo(110). fl . 19,a , - - He+ , . 19,b

. He+, , - (. . 19,a), . , - - , , fi. - , - . (. . 19,b) , 700K, - 900K . - , (. . 19,b). (. . 19,a). - , - (*80% Au *20% Pd). Pd7Au-.491, 492

. 19 , , , - . - . - CO, .489 - CO: 1) CO Pd,2) CO , 3) CO - Pd.493 496 fl . 20 - - CO , Mo(110) 600 800K. , . 19; , . - - , - CO, , . *2030 71 (.495) 2050 2080 71, CO/Pd.494 CO (8 10 .71) (.497) , CO/Au -, (. . 20), . , - Pd7Au , . , - p-. . -s- -

a

0

1000

2000

3000

4000

ISS-,..

Mo Pd Au1300K

1200K

1100K

1000K

900K

800K

700K

600K

500K

400K

Pd/Au/Mo(110)

Au/Mo(110)

0.90 0.95 1.0 1.05 1.10

,

12

0

20

40

60

80

100

Au,.%

200 400 600 800 1000 T, K100

80

60

40

20

0

Pd,.%

b

. 19. Pd(5 fi)/Au(5 fi)/Mo(110) ( 20 ) (a); Au Pd Pd(5 fi)/Au(5 fi)/Mo(110) (1) Au(5 fi)/Pd(5 fi)/Mo(110)(2) (b).488


C2H4 , . , - Pd7Au-, .

Pd(1%)7Au(0.5%)/SiO2 , 5008C.498 - -

Pd(1%)/SiO2 ,499 , 1 ; 96% ( , - 90%-).498 (500 6008C) , - - .500

, - - . , - , . - - . fi - ( ) -. , (, -, ..).

X.

- , , . - , - , in situ.

. Chandler Gil-bertson 501 , - . - - 502. fi - 503 505.

, , -- , in situ, .. - .506, 507

, , - - . fl- 508, 509, . 510. - , .

0

0.0005

0.0010

0.0015

0.0020

0.00252087 71

2105 71

1940 71

,..

.

2200 2100 2000 1900 1800 1700

2200 2100 2000 1900 1800

a

, 71

, 71

0.1%

2087 71

2112 71

b

7

6

5

4

3

2

1

7

6

5

4

3

2

1

. 20. - , Pd(5 fi)/Au(5 fi)/Mo(110), 600 (a) 800K (b) 20 , CO ( ): 0.02 (1), 0.05 (2), 0.10 (3), 0.20 (4), 0.50 (5), 1.0 (6) 2.0 (7).489


511, - -, - (+ ). - - - : -.

X.1. , ,

, C=C C=O, , - - , -. - , C=C*35 .71 512

C=O. , - , .

, 513 Pt/SiO2 (Co7Pt/SiO2 , Cu7Pt/SiO2) (150a). - Pt- ( 2 4.8 10 28%). , . , - C=O, Cu C=C ( 125).

125

Bertero .514 , Pt-- (151) - , - (152), (153) - (154) ( 126).

515 Pt7Co - (decoration) Pt Co - -. Pt, -, -

C=O- C=C Pt-- Pt Co.

, Pt7Co, Murillo .516 -, - (DFT). , C=O Pt7Co7Pt(111) - -s-C7O- - , - (Co) - Pt. - C=O, C=C .

517, , - (150b) , - ( 127). , - , - 2 . Ni 23 139 71 - C=C, - .

127

518 , - Pt- . - Sn : Pt 0.8. , -, - Sn : Pt= (0.2 0.4). Sn 519. ,

O

R

OH

R

O

RH2

758C

Co7Pt

Cu7Pt150a d

R=H (a), Me (b), Ph (c), OEt (d)O

150b

O

H2 (1 ), rt

(111)

(111)

(111)

O

OH

O

OH

151

152

*

154

*

153

126


, Pt- . -, - Pt , - (reductive deposition precipitation).

, C=O , NaBH4 , - . ,520 Rh7Co- C=C , , C=O.

X.1..

- , ,521 - - - , - . - . , - , - .522, 523 , , -, - , , , -, , - .

- Pd7Pb- . - , - () . , . fl-, - . - .524

- C:C . - , , - , -, VIII ( Pd).525, 526

: - , .

fl, Zn Ag Pd- - - , .527

fl - () , b-PdH. . ,

- , , - ? . - , - .528 , , , , - Pd , - , . , .529

. - , . - -, , PdM(OAc)4(OH2)(M=Zn, Ce, Co, Ni).527, 530 , - - .527

- - , - , . , 531 , Ni3Ge/fifi-41 - . 532, 533 - PdGa Pd3Ga7 .

, , , - , , , -. fl, - PdGa- 532, 533 - Pd- -.534 , , . - - PdGa, .

. , PdM(OAc)4(OH2) (M=Zn, Ce, Co, Ni) , , , -


, - -. , PdZn

2-- Pt7Ru/SnO2 , . - - , - - .

, . , ,544 - Rh3Ni - NO2- 4- H2 ( 130). 155 >99% . , Rh3Ni- - NO2- , - , -.

130

, , 545. , Au7Ag , - Au7Ag , - (Metal-OrganicFramework, MOF). - NaBH4 -. , Au7Ag-. , - , (Ag- Au, Aushell Agcore), Au-- Au7Ag .

X.2. -

X.2.. -

( 131). fl Pd ( , ), Pd (. VI.2). , - Pd7M, - , , - .

131

R1 R2 , %

Pd Pd Au

4-Ph H 0 884-Me H 4 100H 4-F 58 1002-NH2 H 0 6H 2-NH2 98 36

- Pd7Au - . 546 - Pd- - Au7Pd, SiO2-. Au : Pd, - . -, Au

, - ArPdIIX-, - 510. , Pd/NiFe2O4 - NiFe2O4 Pd. , , - Pd-, - ' .549 551 552 - Pd/C, Pd7Au/C Pd7Au/SBA-15 (SBA-15 ).

553, Pd PdshellAucore .fi -- - , Pd - , .

3d-, - , Pd7M(M=Ni, Co, Fe) - . , 554 - Pd7Ni - (*10 15 ) . Ni Pd- - Pd-: *90% 808C. , - 40%. -, Pd7Ni Ni Pd50Ni50 , . Pd7Ni - 5 . Ni .

fi - Pd7Co-. 555 PdshellCocore , - . - 95 100% 708C 18 . fi7fl2 (4 : 1), , , H2O 10 20 40% - 20 40 80 90%.

- 556. - , - Vulcan XC-72TM. g-. - () - , Pd(111). - 788C 3 . fl Pd7Cu/C, 96 97%.

- Pd7Cu/C>Pd/C>Pd7Ag/C>Pd7Ni/C. fl : , , .

X.2.. -

, C7C, -, - - - .557 - Pd-.

., 558 Pd7Co-, Pd7Co-, -, - . (258C) ( 132).

132

- . , - Co- , - Pd, , ( 18 85 90%). Pd7Co- 90 96% - 1.5 . Pd-: Pd7Co/ . Pd7Co-- : - 99( ) 93% . Pd7Co-.

Pd7Co- - 559, - Pd7Co- - 808C. - 4 9 .

, - , -

R

HX+Pd7Co

rt, 60 100

R(91 99%)

R=Me, OMe, NO2; X=I, Br, Cl


. 560 - Pd7Cu , - (fifi). - fi, fi . - Pd7Cu - ; 97% 658 3 . fifi@Pd+fifi@Cu 25%. , Cu , - ; , , .

Pd7Cu/C , - , , 561. , Cu : ( 133).

133

Pd7Cu- 562, 563.

X.2..

- - Pd. C7C HHal ( 134).

134

, - Pd0. - Pd0 , . Pd0 - , , , , . - ., , - , , , - , .

, . - -.

, 564 - - ( 135). fl Pd,Ag, Pd7Ag, Pd7Ni Pd7Cu - . *15 , - -. - - ( fifl, 1008C, 18 )., : Pd7Cu (4 : 1)>Pd44Pd7Ni (1 : 1)>Pd7Ag (1 : 1)>Ag. fl - Pd :Cu=4 : 1 91%, 74%.

135

Pd7Cu- - -, . 22%, 5 6 , . Pd7Cu- - - ( - Ac, CN) ( OMe, CHO, Ac, NH2 , OH, CO2H). - 66 100%, -.

Kim .,556 - Pd7M ( M=Ag, Ni, Cu), - (Vulcan XC-72TM). - - . - Pd7Cu/C. , , - .

X.2..

- - ( ) 565. 100 3608C Cu, - - ( 136).

AR2

X

AH

+ R2[Pd], [Cu]

X = I, Br; A = O, NR1

R2R1 X +

R2R1R1

R2 + + B .HX

R1=Ar, CH=CH2; R2=Ar, CN, Ac; X=Cl, Br, I

cat

B

I

+7HI


136

565 Au7Pd-, - , fi7H2O (1 : 2) Ar 358C 12 24 . , fi , . - : Au0.5Pd0.5 96%, Au : Pd - . fi . , - 566 - .

565 - , 2-- . , , , Au7Pd- - , ., - Pd , . fl, - . , - Pd - .

XI.

III VI, - - . , , . (fi), . , .

- . - - fi .

fi , (, , , - .) () (- , , , , , , ..). , 2010 . . .fl fl -

, .

-- . - , - (. 21). , 568. , ( , -, , ) - . fi, , - (. 22), fi.

fl fi , , fi (fi) - , .

, . , - (fi),

Ar1 Hal + Hal Ar2Cu

7CuHal2Ar1 Ar2

(): ,, ..

sp

1

. - fi . fi - , - ().

XI.1.

- . fi , - - . , fi - , ,- - , ( O2 H2O2) , , ,- , , , , .569 573

- :1) ,2) , 3) , 4) () , 5) . - , .

( ) , ; , -, - - . fi , - - fi ( , ).

( - , ), --, -, -- - , - - . fi ( (O.Warburg, 1921 1923 .) '(S.Zylbertal, 1931 .) - - ).570 - fi .

, , -, fi, - - . - ( - , , ), ( ) .573, 574 fl , -- fi . -- fi , - - (- ) (, ) - , . , , - - fi - . -, - .

fi - -. N- (156) - N- (157) , Monsanto - Round-up ( 137).571

137

S=400 1000 2 . 71, '. ' , 9008C - NH3 , , ' , g- , , . , , - O2 .

fi ( , ,

(HO)2(O)P N CO2H

HO2C

156

(HO)2(O)P NH2(HO)2(O)P N CO2HH

157

, 1508

7H2CO,7CO2

, 1508

7H2CO,7CO2


.) CO Cl2 . 130 , 2000 . DuPont - .575 , - , - CCl4 ( 50 ppm) 10 . (808C, 4.83 ) - .

- -

(. 1). -, - fi (B, N, Si, S, P .), .576, 577 , - , - (, - ). fi - , : ( - -

1. .

fia

, fi, fifl, fi 0.5 0.7 ( ( ) , , ); -

;

, ()

-

fifl p- O2+HNO3

- ( )

H2O2

p- H2O2 , O3 O2 , O- N-- H2O () '

'

'

fi N- '

-

fi

, , N- ' N- ()

, , , (, ) =N7H, PhC(CH3)=CH2

, , , (, )

a ( ), (), fi , fifl .


), ( -), ( ), (), ( , , one-pot-).

fl - (C-SO3H) ( - ) - , fl.578

, - - , 1,3- - 80 94% ( 138).579

138

--2(1H)- ( -) b- , ( ) ( 139).580 5 6 -.

139

- . , - - . fl, N- g- Norit RX-1.5 Extra, ( , , 0.08 .%), - (2450 fi, 600 ,5 ) 1158C 70%-

100%, - 1 - 50% 100%( 140).

140

, , , - - - - , -, .

XI.2.

, -, - . , ,. . 2 - , - VIII , fi (M/C), . 3 Pd/.

- C=C C:C, C7C - VIII .

XI.2.. fl fi/

M/C, - , , , 5 .%. ' , - fi. - 569, 581.

fl - - - . , - ( - 2 200 ) - , , - . , - - ( , - ) 582, 583 -

EWG

N

N

O

R

OO

O

+ +

H

C-SO3H

EtOH, D

N

O

R

ONH2

EWGO

H

EWG=CN, CO2Et

N

NH

R0

X

EtO

O

RH

EtO

O

R

O

+

R0

O

H

+

H2N

H2N

XC-SO3H

1408C

X=O, S

NH+

O

O

H

C6H13-nCs+/C

108 1158CN

O

C5H11-n


, - - . - , .

fi - , 7.584

fi , - - , .

Pt/C- Pt () . - Pt/C -, 40 80 .%.585 590

- Pt/C ()

2. M/C.

fi

Pd Pt Ni Ru Rh Os

+ + + + + +

, + + + + + + C=C C:C + + + + + + C=C + + + + + C=O + + + + + C=N, C:N + + + + C7C, C7O + + + + C7N, C=N, C:N, N:N + + HHal (Hal=Cl, Br, I) + + , NOH, NO, NO2 , H2O + + + + + + + + + +

(, , , + + + , .)

CO (, ) + +

( ) + + + + +

+ + + + + + () +

- + + + +

, . +()- () + +

( ) + + + +

3. Pd-- , .

-

-

(- , ) - - ; - -

- (, , )

V.P.Ananikov