Download pdf - conrotatory Metal Catalyzed Cyclization … · conrotatory Metal Catalyzed Cyclization oof pEenynesning? ... A. Fürstner, N. Chatani, M. Malacria, A. S. K. Hashmi, F. D. Toste, F

ZR

[M]+

Z

R'

Alder-ene cycloisomerization

Z

R =

Z = NTs, O

Z

R

Z

R

Z

R

Skeletal Rearrangement

ZR

R'OHOR'

Alkoxycyclization

conrotatory opening?

Metal Catalyzed Cyclization of Enynes

B. M. Trost

P. A. Wender

A. Fürstner, N. Chatani, M. Malacria, A. S. K. Hashmi, F. D. Toste, F. Gagosz, S. Kozmin, S. P. Nolan

Metal-Catalyzed Skeletal Rearrangement of Enynes: Mechanistic Pathways

MXn

RZ

Z

H

R

H

MXn

Z

R

Z

R- MXn

+

singlecleavage

doublecleavage

Z

H

- MXn

R

H

conrotatory opening

Z MXn

HR

H

- MXn

Z

R

MXn

Z

H

- MXn

R'

Metal-catalyzedAlder-enecyclosiomerization


Chem. Eur. J. 2003, 9, 2627.

TSexo

10.3

19.5O

C

C

ClC

Pt

C

Cl

C

C

C

C

CC C

C

C

C

C

Cl

C

Pt

O

Cl

C

C

CC

C

C

O

C

Pt

Cl

C

Cl

HMe

Pt

Cl

Cl

OH2

=

exo

TSendo

11.2

8.1

Cl

O

Pt

C

C

C

C

C

C

C

C

Cl

ClO

Pt

C

C

C

C

C

Cl

C

C

C

endo


MXn

Z

H

R

H

MXn

RZ

a

b

Z

HOR'

HR

Z

R

OR'

5-exo-dig

a

R'OH

R'OH

b

RZ

MXn

Z

MXn

H

H

R

H

Z

H

H

R

H

Z

H

OR'

HR

Z R

OR'

b a6-endo-dig

R'OHa

R'OH

b

Chem. Eur. J. 2003, 9, 2627

Pt(II) vs. Au(I) as Catalysts

TSexoTSendo

10.3

19.5

11.2

8.1exo

endo

Pt(L)Cl2

Pt(L)Cl2Cl2(L)Pt

Pt(L)Cl2

Cl2(L)Pt

L = H2O

PtCl2

TSexo

TSendo

0.1

exo

endo

Au

Au

PH3

Au

H3P

AuPH3

AuH3P

[Au(PH3)]+

PH3

6.2

13.4

6.1

Au(I)-Catalyzed Cyclization of Enynes: Alkoxycyclizations

Angew. Chem. Int. Ed. 2004, 43, 2402.

Ph3PAuMe, TFA

MeOH, 23°C, 30 min

(95%)

MeO2C

MeO2C

OMe

MeO2C

MeO2C

OMe

OMe

Ph3PAuMe, H3PW12O40

MeOH, 56°C, 17 h

(96%)

PhO2S

PhO2S

PhPhO2S

PhO2SOMe

Ph

HO

Ph

Ph3PAuMe, H3PW12O40

toluene, 23°C, 3 h

(100%)

O

HPh

H

Au(I)-Catalyzed Cyclization of Enynes: Skeletal Rearrangements

Angew. Chem. Int. Ed. 2004, 43, 2402.

CH2Cl2, 23°C, 10 min

MeO2C

MeO2CMeO2C

MeO2C

(96%)


(91%)

MeO2C

MeO2C

MeO2C

MeO2C


PhO2S

PhO2SPhO2S

PhO2S

Ph3PAuCl / AgSbF6

Ph3PAuCl / AgBF4

Ph3PAuCl / AgBF4

Ph3PAuCl / AgSbF6


(67%)

MeO2C

MeO2C

MeO2C

MeO2C OH

OH

(100%)

New Au(I) Complexes

C. Nieto-Oberhuber

N NR R'

R = R' = MesR = Mes, R' = MeR = R' = Me

Au

Cl

R = Cy, R' = HR = t-Bu, R' = HR = Cy, R' = i-Pr

P Au Cl

R R

R'

R'

R'

P Au Cl

Cy Cy

MeO

MeO

R = Cy, t-Bu

P Au NCMe

R R SbF6

New Au(I) Complexes

R = Cy, t-Bu

P Au (ArH)

RR SbF6

Angew. Chem. Int. Ed. 2006, 45, 5455.

New Au(I) Complexes

electrophilicity

AuCl

N NR R'

R = R' = MesR = Mes, R' = MeR = R' = Me

Au

Cl

/ AgSbF6R = Cy, t-Bu

P Au NCMe

R R SbF6

[Au(PPh3)(MeCN)]+SbF6-

O P3

Au Cl

/ AgSbF6

Metal-Catalyzed Skeletal Rearrangement of Enynes: Mechanistic Pathways

- [Au(PH3)] Me

single cleavage

Ea = 0.1 kcal·mol-1

!G = -0.7 kcal·mol-1

- [Au(PH3)]

Me

double cleavage

Me

H

AuH3P

B3LYP/6-31G(d), LANL2DZ (Au) (E kcal mol-1).

Au

transition state for the double rearrangement

Au

H3P

Me

H

Au

PH3

MeH

H

Me

[Au(PH3)]

Ea = 9.1 kcal·mol-1

!G = 2.7 kcal·mol-1

Angew. Chem. Int. Ed. 2005, 44, 6146.

Au(I)-Catalyzed Biscyclopropanation of Dienynes

H


R

R R

R


R = CO2Me (98%)

R = SO2Ph (100%)

R = CH2OAc (96%)

(2 mol%)

HMeO2CCO2Me

MeO2C

MeO2C

MeO2C

MeO2C

CO2Me

CO2MeCH2Cl2, 23°C, 5 min


(2 mol%)

(88%)

Chem. Eur. J. 2006, 12, 1694.

Au(I)-Catalyzed Biscyclopropanation of Dienynes

Chem. Eur. J. 2006, 12, 1694.

L-Au

L-Au

H

H

H

1.8

6.6

2.9

13.2

anti

Au(I)-Catalyzed Intermolecular Cyclopropanation

Ph

H

MeO2C

MeO2C MeO2C

MeO2C

Ph

H+

CH2Cl2, -40 to 0°C

(94%)

N NMes Mes

AuCl / AgSbF6

PhH

H

H

(77%)

PhH

H

H

(76%)

Ph

H

H

(60%, 5:1)

TsN

PhH

H

H

(75%)

TsN

PhH

H

H

(73%)

Me

H

(53%)

MeO2C MeO2C MeO2C

PhO2S

MeO2C MeO2C MeO2C

PhO2S

Angew. Chem. Int. Ed. 2006, 45, anie.200602448.

H

Au(I)-Catalyzed Intermolecular Cyclopropanation

Au(L)

R

R

R

- Au(L)+

R

(L)Au

H

H

Au(L)

R

H

H

Au(L)

RH

H

- Au(L)+


tBu

tBu

O P AuCl3

/ AgSbF6

-50 to 23°C

ZZ = C(CO2Me)2

Ph

Z

Ph

(67%, 3.3:1 cis/trans)

Au(I) Metallotropic Shift

Z

[AuL]Z

MeH

Z

Z

MeH

[AuL]

Me Me

[Au(L)]

[1,3]-Metallotropic shift


CH2Cl2, 23°C

/ AgSbF6

tBu

tBu

O P AuCl3Z

Z = C(CO2Me)2

2 : 1

Z

Z

H

Z

Me

Me

H

Z

H

Z

Me

Me

H

Me Me

+(2 mol%)

[4+2] Cycloaddition of Arylenynes

J. Am. Chem. Soc. 2005, 127, 6178-6179

Z

R1

Z

HCH2Cl2, r.t.

R1R2

R2

R3

R3[Au(L)Cl], AgSbF6

H

MeO2C

MeO2C

(86%)

H PhH

MeO2C

MeO2C

(67%)

H

MeO2C

MeO2C

(77%)

OMeH

MeO2C

MeO2C

(74%)

NO2

H

MeO2C

MeO2C

(95%)

H

MeO2C

MeO2C

(65%)

OMe

H PhH

MeO2C

MeO2C

(80%)

Ph

H PhH

MeO2C

MeO2C

(58%)

NO2

H

MeO2C

MeO2C

(73%)

Cyclopropane to Cyclobutanone Ring Expansion

Z

HH

OR

[Au(L)]

Z

H

H

[Au(L)]

OR

- [Au(L)][Au(L)]

CH2Cl2, MeOH (2 equiv)r.t., 5 min

P Au NCMet-Bu t-Bu SbF6

OR

O

H

H

E. Jiménez-Núñez, C. Claverie

R = TMS (98%)R = TBS (100%)

MeO2C

MeO2C

MeO2C

MeO2C

Cyclopropane to Cyclobutanone Ring Expansion and Prins Cyclization

CH2Cl2, r.t., 5 min

P Au NCMet-Bu t-Bu SbF6

E. Jiménez-Núñez, C. Claverie

Z

OEt

Z O

H

H

Z = C(CO2Me)2 (11%) (69%, anti/syn = 1.3:1)

Z = --- (54%, anti/syn = 3.2:1)

+ ZOEt

HH

O

O

H

H

OH

OH

O

Sulcatine G

Z

HH

OEt

[Au(L)]

PrinsZ

OEt

HH

[Au(L)]

Gold-Prins Reaction

Angew. Chem. Int. Ed. 2006, 45, 5452.

CH2Cl2, rt, 30 min

Z = C(CO2Me)2

ZO

HZ

H

O ZO

MeMe

Me

HH

+

(58%) (18%)

AuCl

Z

HMe

ClAu

O

H

AuCl

Z

H

O

Me

AuClH

Z

H

O

Me

H

AuCl

- AuCl

Gold-Prins Reaction

O

Me

Me

Me

OHH

HOMe

H

Orientalol E

CH2Cl2, rt, 30 min

AuClZO

MeZ

H

O ZO

MeMe

Me

MeMe

+

(79%) (10%)

ZO

i-PrZ

H

O ZO

MeMe

Me

i-Pri-Pr

+

(84%) (12%)

CH2Cl2, rt, 30 min

AuCl

Z

Me

O

Me

Me

[Au(L*)L']SbF6

CH2Cl2, rt, 5 min

Angew. Chem. Int. Ed. 2006, 45, 5452.

P Au NCMe

t-But-Bu SbF6

[Au(L*)L']SbF6 =

Arylation of Alkynes

AuCl3CH2Cl2, 23°C, 1 h

NH

N

R SO2Ar

R = CO2Me, Ar = 2,4-(NO2)2C6H3 30 min (75%)

R = H, Ar = Ph 24 h (55%)

N

N

O

MeO

CO2Me

Lundurine A

Angew. Chem. Int. Ed. 2006, 45, 1105.

NH

N SO2Ar

NH

NSO2Ar

CH2Cl2, 23°C

P Au NCMe

t-But-Bu SbF6

(5 mol%)R R

R = CO2Me, Ar = 2,4-(NO2)2C6H3 30 min (82%)

R = H, Ar = Ph 16 h (65%)

Arylation of Alkynes

Catelijne Amijs, Cati Ferrer

NH

N Ts

Me

Me

NH

NTstoluene, 90°C, 48 h

P Au NCMe

t-But-Bu SbF6

(5 mol%)

(58%)

NMe

O

Me

Me

NH

O

(36%)

NMe

OHMe

(27%)

toluene, 90°C, 24 h

P Au NCMe

t-But-Bu SbF6

(5 mol%)

+

MXn

RR R

R

MXn

ZR

H

Z

HOR'

RH

Au(I)

Z

H

H

R

Au(I)

Z

R

OR'

and / orR'OH

Z