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Ready; Catalysis Hydroformylation

Ready; Catalysis Hydroformylation Asymmetric Hydroformylation: under-developed

OH

OH

4 stepshigh yield PPh2

OH

O

OPCl PPh2

O

O

PO

(S,R)-BINAPHOS

R

0.5-0.1 mo% Rh(acac)(CO)2BINAPHOS (4x [Rh])H2/CO (100 atm)

R

CHO

HayashiJOC, 1993, 1945

n:i selectivity "beyond the discussion here"Nozaki, JACS, 1997, 4413

R

Ph

4-OMe-Ph

4-ClPh

PivO

4-CF3-Ph

N

O

O

% ee i:n

92

88

93

93

93

85

88:12

87:13

87:13

96:4

88:12

89:11

O

CH3

CH3 O

CH3

CH3OHC

O

CH3

CH3

CH3H3C

O

OH

OH

HHO2C

(+)-Ambruticin Jacobsen, JACS, 2001, 10772

91:9 i:n96:4 d.r.

R

R'

R

R' CHO

*?

see Breit, Eur. JOC, 1998, 1123,Buchwald, JACS, 2011, 19080


O 1. H2N-NH2

2. succinyl chloride,PH2

PH2

NN

PNN

P

O

O

O

OCO2H R

RR

R

~30%

(±)-

R = CO2H

A: R =O

NH

(resolve diastereomers)

R

500 psi H2/CORh(acac)CO2/A (0.02 mol%)

60 oC CHOR

CH3

CH3

CHO

30:1 b:l100% conv89% ee

CH3

CHO AcO

CH3

CHONC

4.8:1 b:l100% conv87% ee

40:1 b:l100% conv95% ee

Landis, Klosin, JACS, 2005, 5040Stahl, Landis, JACS, 2010, 14027

HN

CH3

CHO

33:1 b:l99% conv99% ee

BocHN

CH3

CHO

51:1 b:l99% conv94% ee

Cbz

CH3

CHO

2:1 b:l99% conv96% ee

TBSOCH3

CHO

4.4:1 b:l99% conv86% ee

BzCHNCH3

CHO

7:1 b:l99% conv93% ee

AcO

OAc

Ready; Catalysis Hydroformylation-4

Ready; Catalysis Hydrosilylation

Note in some cases X-Si bond formation precedes H-C bond formation

Hydrosilylation

What:R

H-SiR3

catalyst

RSiR3

OR ORSiR3

catalyst usually = Pt, Rh, Pd, Ir

why:R

SiR3 [O]R

OH

To retire rich, young and famous:

R ROH

R

OHorH2O+

H-OH 120C=C 60O-C -90C-H -100

!H ~ -10 kcal/molOR

SiR3 = protected alcohol

How: Mn

Mn+2

SiR3

H

Mn+2

SiR3

H

X

Mn+2

SiR3

X

H

XSiR3

H

HSiR3

X

or as adhesives, surfactants(major applications industrially)


Platinum [very active, Pt(II) - Pt(IV)]2007: 5.6 metric tons of platinum used for hydrosilylation

H2PtCl6 6H2O0.005 mol%MeCl2Si-H



SiCl2Me

93%

SiCl2Me

98%

SiCl2Me

Has been suggested that Pt colloids are the real catalyst. These are suspensions of fine particles 10-1000 A radius. These solutions appear homogeneous and are able to pass through filters.

quant.

BnO H

OSiMe2H

10 mol% HMDS2 mol% H2PtCl6 6H2O>80 %yield

BnO H

O SiMe2

8 stepsH

OO

OJatrophatrionePaquette, JACS, 2002, 6542

O

HOBn

OMeO

O

OH

1. (Me2HSi)2NH;H2PtCl62. TBAF

O

HOBn

OMeO

O

OH

87:13

54%

Leucascandrolide AKozmin, OL, 2001, 755

LnCu Cl

LnCu OtBu

H SiR3

LnCu OtBu

H SiR3

LnCu H

O

O

CuLn

H

OCuLn

H

tBuOSiR3

H SiR3

KOtBu

OSiR3

H

OMe

MeO

MeO

MeO

OO

O

ClMg Me

EtO2C(formed in situ from iodide) OMe

MeO

MeO

MeO

OO

O

O

MeO-BIPHEP, NaOtBu (1.2 equiv)PMHS, tBuOH>85%, 93%ee

OMe

MeO

MeO

MeO

OO

O

O

NaHMDS, MeI

OMe

MeO

MeO

MeO

OO

O

O CH3

Buchwald, ACIE, 2005, 6177

(±)-

Cu-Catalyzed Hydrosilylation: Mechanism and Application

BnO

OSi

H Rh(acac)(CO)2, CO; H2O2, KF, MeOH

BnO

OH O OH

1 pot, 3 stereocenters, 2 oxygens, 2 C-C bonds67%, 15:1 dr 6 steps

BnO

OTBS O O

O

OH

Rh(acac)(CO)2CO/H2

BnO

OTBS O O

O

O OH >94%

8 steps

OH OH OH

O OMe

O

H

OHJACS, 2011, 7308

Ready; Catalysis Hydrozirconation

Ready; Catalysis Hydroacylation

Ready; Catalysis H-X Additions to Olefins

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