Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe...

Carbon Monoxide “Insertion”

Siyu Ye

2008.1.25

22

The term “insertion” is used to describe the process whereby an

unsaturated moiety, which may or may not be coordinated to the

metal initially, becomes bonded to the metal and to a saturated ligand

(which was initially attached to the metal center).

M X

M A B XA B

C

M C X

Anderson, G. K.; Cross, R. J. Acc. Chem. Res. 1984,17, 67.

Y M XY M C X

O

Y C X

OCO

33

Content

1. Introduction

2. Acid Induced Carbonylation

3. Main Group Metal Induced Carbonylation

4. Transition Metal Induced Carbonylation

5. Conclusion

Background

Methanol Carbonylation

Hydroformylation

Double Carbonylation

44

Content

1. Introduction




5. Conclusion

Background


Hydroformylation


5

The CO Molecule

C+O-, electronegativity

C-O+, a low dipole moment of 0.112 D

Molecular Orbital of Carbon Monoxide

C O

C O

C O

C O

C O

n

*

*

Henrici-Olivé, G.; Olivé, S. The Chemistry of the Catalyzed Hydrogenation of Carbon Monoxide; Springer-Verlag: Berlin, Heidelberg, New York, Tokyo, 1984; p 23.

5

LUMO

HOMO

6

M X

M X

CO

M X

CO

M C X

O

M C X

OX migration

CO migration

CO

Migratory Insertion

Which is more appropriate?

77

Calderazzo, F. Angew. Chem., Int. Ed. 1977, 16, 299.

Brunner, H.; Vogt, H. Angew. Chem., Int. Ed. 1981, 20, 405.

FeOCMe

LFeOC L

O

Fe LO

CO

Mn

CO

O

13COOC

OC COMn

CO

COMeOC

OC COMn

CO

CO13COOC

Me COMn

CO

CO13COOC

OC Me+ +

A B C

(A:B:C = 1:1:2)

Mn

CO

COMeOC

OC CO13CO Mn

CO

O

13COOC

OC CO+alkyl migration

CO migration

88

Influence Factors

Cavell, K. J. Coord. Chem. Rev. 1996, 155, 209.

cis-(CO/Me)

trans-(P/Me), ligand with a large trans influence

θ, angle of L-M-X

partial negative charge at alkyl group

partial positive charge at CO

Pt

Me

CO

PH3

F

Pt

Me

CO

PH3

F

Pt C

PH3

FMe

O

9

Absence of Acyl-to-CO Migration

Ni-C (acetyl) bond (184 pm) < Ni-C σ bond (194 pm)

Ti-C (acetyl) bond (207 pm) < Ti-C σ bond (214 pm)

M-C (acetyl) bond, a partial double bond

9

Henrici-Olivé, G.; Olivé, S. The Chemistry of the Catalyzed Hydrogenation of Carbon Monoxide; Springer-Verlag: Berlin, Heidelberg, New York, Tokyo, 1984; p 79.

Ni

P(CH3)3

Cl

P(CH3)3O

Ti Cl

O

Mn(CO)5O Mn(CO)5

O

O258 atm CO

80 oC

O

Cl

O

NaMn(CO)5 Mn(CO)5O

O

Mn(CO)5O

CH3Mn(CO)5+ +decomposed

1010

Content

1. Introduction




5. Conclusion

Background


Hydroformylation


1111

R OH COOHRCO, H2O

H+

R OH R OH2+ R

R R CO+ COOHR

H+

H2O -H+CO

OCO

HF-TaF5

+OC

OH O

H+ CO

-H+

Koch carbonylation

Farcasiu, D.; Schlosberg, R. H. J. Org. Chem. 1982, 47, 151.

Acid Induced Carbonylation

1212

Content

1. Introduction




5. Conclusion

Background


Hydroformylation


1313

Li Induced Carbonylation

n-BuLi + CO n-BuC(O)Li n-BuC(O)SiMe3-110 oC Me3SiCl

77 %

Seyferth, D.; Weinstein, R. M. J. Am. Chem. Soc. 1982, 104, 5534.

Song, Q.; Chen, J.; Jin, X.; Xi, Z. J. Am. Chem. Soc. 2001, 123, 10419.

I

IO

Ph

Ph

73 %

1) 4 eq t-BuLi, -78 oC, 1h2) CO, -78 oC, 1h

3) 2 eq PhCH2Br, -78 oC to r.t., 1h

1414

Mg Induced Carbonylation

EtMgBr

Et MgBr

O

Et Et

OEt

OMgBr

Et

MgBr

Et2CHOHEt

O O

MgBr

Et

O O

Et Et

O OH

Et

Et

O OMgBrMgBr

Et

COHMPT

EtMgBr

EtMgBr

H2O

H2O

EtBr

EtBr

CO

Sprangers, W. J. J. M.; Louw, R. J. Chem. Soc., Perkin Trans. 2 1976, 1895.

HMPT = PNN

N

15

Al Induced Carbonylation

15

2 t-Bu3Al 2 CO Alt-Bu

Ot-Bu

t-Bu

Alt-Bu

Ot-Bu

t-Bu

+20 oC

hexanes

Mason, M. R.; Song, B.; Kirschbaum, K. J. Am. Chem. Soc. 2004, 126, 11812.

1616

Content

1. Introduction




5. Conclusion

Background


Hydroformylation


17

Transition Metal Induced Carbonylation

17

Chiusoli, G. P. Acc. Chem. Res. 1973, 6, 422.

X COO

O+

Ni(CO)4 or Pd(0)

MeOH

M

O

M

R

O

X

M X

M X

CO

X

X

CO

1818

Heck, R. F. J. Am. Chem. Soc. 1963, 85, 2013.

HH + CO + H2OOH

O

Ni2+,Cu2+

8~12 MPa, 150~250oC

Reppe process

Schoenberg, A.; Bartoletti, I.; Heck, R. F. J. Org. Chem. 1974, 39, 23.

R CO HXR

O

OR'+ +

Ni(CO)4

R'OH

BrO

O

Bu

PdBr2(PPh3)2, CO,n-BuOH, n-Bu3N

100 oC, 1 atm

19

CO-to-C—X Insertion

1919

Heck, R. F. J. Am. Chem. Soc. 1963, 85, 1460.

HCo(CO)4 CO (CH2)2COCo(CO)4R

R

OH

O O

O+ +

N(Cy)2Et+ (Cy)2N+HEt Co(CO)4

-

Wang, M. D.; Alper, H. J. Am. Chem. Soc. 1992, 114, 7018.

N R

R'

N

N

R'

O R

R'

O

R

R' = Me, Ph, CH2Ph, CH2OCH3, CH2COOEt

(30~61%)

(15~56 %)

Co2(CO)8

CO, 54 atm, 220 oC

R = alkyl

R = aryl

2020

Pauson-Khand Reaction

NTs N OTs

10 mol% PdCl210 mol% tmtu

1 atm CO, THF50 oC, 36 h, 92%

N N

S

tmtu =

Tang, Y.; Deng, L.; Zhang, Y.; Dong, G.; Chen, J.; Yang, Z. Org. Lett. 2005, 7, 1657.

OTBDPS

Co2(CO)6

O

H HH

OTBDPS

triquinane

6 eq. TMANO (anhydrous)

CH2Cl2, -78 oC to r.t. 85%

TMANO = N O

Paquette, L. A.; Borrelly, S. J. Org. Chem. 1995, 60, 6912.

Co2(CO)6

+

O

2121

Complicated Carbonylation

Negishi, E.-I.; Coperet, C.; Ma, S.; Mita, T.; Sugihara, T.; Tour, J. M. J. Am. Chem. Soc. 1996, 118, 5904.

Aksin, O.; Dege, N.; Artok, L.; Turkmen, H.; Cetinkaya, B. Chem. Commun. 2006, 3187.

R

R

B(OH)2

R'

O

R'

RR

O

[Rh(cod)Cl]2 20 atm CO

toluene80 oC,16 h

+

I

OSiR3 OSiR3

O

75 %, trans/cis = 3:1

PdCl2(PPh3)2, MeOH

15 bar CO, 100 oC

OMeO

2222

Me

BnO

O

MeMe

BnOCO+

5 mol% [Rh(cod)Cl]2 10 mol% DPPP

p-xylene130 oC, 2.5 h

(1 atm)

84 %

Matsuda, T.; Tsuboi, T.; Murakami, M. J. Am. Chem. Soc. 2007, 129, 12596.

Kramer, J. W.; Joh, D. Y.; Coates, G. W. Org. Lett. 2007, 9, 5581.

OR'

R

OHO

RR' O

OH

CO2 mol% HCo(CO)4

1.0 M DME60 oC, 24 h

+

(800 psi)

23

Wang, Y.; Wang, J.; Su, J.; Huang, F.; Jiao, L.; Liang, Y.; Yang, D.; Zhang, S.; Wender, P. A.; Yu, Z.-X. J. Am. Chem. Soc. 2007, 129, 10060.

X

O

X

[Rh(CO)2Cl]2, COdioxane, 80 oC

ArICO2EtH

N2

CO2Et

N2

Ar

O

+

10% Pd(PPh3)4, Et3N, Bu4NBr,

CO balloon,MeCN, 45 oC

Peng, C.; Cheng, J.; Wang, J. J. Am. Chem. Soc. 2007, 129, 8708.

2424

Content

1. Introduction




5. Conclusion

Background


Hydroformylation


2525


Forster, D. J. Am. Chem. Soc. 1976, 98, 846.

CH3OH + CO CH3COOH

CH3COOH CH3OH+ CH3COOCH3 + H2O

CH3COOCH3 + CO (CH3CO)2O

RhI

I CO

CO

RhI

I CO

CO

CH3

I

RhI

I CO

COI

H3C

RhI

I CO

CO

CO

I

CH3CO

CH3COI

CH3I

H2O/CH3OH

CH3COOH/CH3COOCH3

slow

Monsanto process

2626

RhI

I CO

CO

RhI

I CO

CO

CH3

I

RhI

I CO

COI

H3C

RhI

I CO

CO

CO

I

CH3CO

CH3COI

CH3I slow

CH3COOCH3

(CH3CO)2O

slow

殷元骐主编 , 《羰基合成化学》 , p 167.

RhI

I CO

CO

RhI

I CO

CO

CH3

I

RhI

I CO

COI

H3C

RhI

I CO

CO

CO

I

CH3CO

CH3COI

CH3I slowCH3COOCH3

(CH3CO)2O

CH3COOLiLiI

27

Hydroformylation

27殷元骐主编 , 《羰基合成化学》 , p 4.

RR

OR

O

CO H2cat

+ + +

n iso

HCo(CO)4 HCo(CO)3

-CO

+CO

HCo(CO)3

O

(OC)3Co

CO

H2

H

O

(OC)3Co

(OC)4Co

(OC)3Co

(OC)4Co

O

(OC)3Co

O

H

H2

CO

iso

n

typical condition: 110~180 , 20~35 MPa℃double bond isomerization, 110 , p(CO) = ℃ 9.0 MPa, 1-pentene vs. 2-pentene, the same

n/iso ratio100 , p(CO) from 0.25 MPa to 9.0 MPa, ℃ n/iso from 1.6 to 4.4high p(CO), high p(H2)

2828

Jackson, W. R.; Perlmutter, P.; Suh, G.-H. J. Chem. Soc., Chem. Commun. 1987, 40, 129.Couthino, K. J. et. al. J. Chem. Soc., Dalton Trans. 1997, 3193.

PPh2

PPh2

OHRh2(OAc)4/PPh3 CO/H2

86%

O

O

O

O+

Rh-TPPTS CO/H2

HO OH

Nair, V. S. et. al. Rec. Adv. Basic Appl. Aspects Industr. Catal. 1998, 113, 529.

TPPTS = P(m-C6H4SO3Na)3

OH

O OMeCO/H2(1:1), MeOH Rh6(CO)16/PPh3

63-84 bar, 150 oC

Smith, W. E. et. al. In Catalysis of Organic Reactions; Augustine, R. L., Ed.; Dekker: New York, 1985; p 151.

2929

NR2

HNR2+

CO/H2(1:1) [Rh(cod)Cl]280 bar, 20 h, 80 oC

81-93%

HNR2 = diethylamine, morpholine

Kranemann, C. L.; Eilbracht, P. Synthesis 1998, 71.

R3R2

R1

R3R2

R1

O

R3R2

R1

OH

R3R2

R1

O

OH

R3R2

R1

O

CO/H2(1:1) RhCl(PPh3)3

100 bar, 70 h, 130 oC

a: R1 = CH3, R2 = R3 = H, 21% b: R1 = H, R2 = R3 = CH3, 40%

Roggenbuck, R.; Eilbracht, P. Tetrahedron Lett. 1999, 40, 7455.

3030

Asymmetric Hydroformylation

Breit, B. Acc. Chem. Res. 2003, 36, 264.

Sakai, N.; Mano, S.; Nozaki, K.; Takaya, H. J. Am. Chem. Soc. 1993, 115, 7033.

Difficulties : 1. High regioselectivity

2. High enantioselectivity

3. No racemization of aldehyde

RR

OR

O

+

Rh(I)/L*CO/H2

linear branched

R = Ph 12 : 88 (94% ee)R = Et 79 : 21 (83% ee)R = OAc 14 : 86 (92% ee)R = 13 : 87 (96% ee)

L* = (R,S)-BINAPHOS

PPh2O

PO

O

3131

Diastereoselective Hydroformylation

Breit, B.; Zahn, S. K. Angew. Chem., Int. Ed. 1999, 38, 969.

O O

PPh2

R

R

O(o-DPPB)

O

R

O(o-DPPB)

O

+

Rh-cat.CO/H2

55-99%

syn anti

96 : 4up to

Breit, B. Angew. Chem., Int. Ed. 1996, 35, 2835.

R

O(o-DPPB)

R

O(o-DPPB)

O

R'

36-70%

R

O(o-DPPB)

O

R'R

O(o-DPPB)

OWittig olefination

hydroformylation hydrogenation

0.7 mol% RhH(CO)(PPh3)3, 1.1 eq Ph3P=CHCOR', 20 bar CO/H2(1:1), toluene, 90 oC, 48 h

syn:anti 90:10

32


32

R X + 2CO + NuH R

O

O

Nu + HXCo or Pd cat.

NuH = R'NH2, R'OH, H2O

殷元骐主编 , 《羰基合成化学》

(Rhone-Poulenc Company)

ArCH(CH3)X + CO ArCH(CH3)COCOOH + ArCH(CH3)COOH + ArCH2CH2COOHCo2CO8, base

R'OH, H2O

X = Cl, Br, Ibase = Ca(OH)2, NaOH, LiOHmild condition: r.t. 0.2 MPa

CH2X+ CO + Ca(OH)2

5.0 MPa, 60 oC

Co2(CO)8, R'OH HCl OH

O

OOH

O+

R RR

X = F, Cl, Br, IR = H, X, CN, alkyl, aryl

33

CH2ClCo(CO)4

- Co(CO)4+

Co(CO)4

O

OH

O

Co(CO)4

OH

OH

Co(CO)4

O

O

O

OH

CO

CO

OH-

OH-

Cassar, L. Ann. N. Y. Acad. Sci. 1980, 208, 333.Alper, H. Adv. Organomet. Chem. 1981, 19, 183.

3434

ArX + 2CO + R2NH ArCOCONR2 + ArCONR2

PdCl2(PR3)2

50~100 oC, 1~4 MPa

Kobayashi, T.; Tanaka, M. J. Organomet. Chem. 1982, 233, C64.Ozawa, F.; Soyma, H.; Yamamoto, T.; Yamamoto, A. Tetrahedron Lett. 1982, 23, 3383.

Pd(0)

PdAr X

Pd XO

Ar

Pd XO

Ar CO

PdO

Ar

O

NR'2

Ar

O

O

NR'2

PdAr X

CO

PdArO

NR'2

Ar

O

NR'2

2R'2NH

R'2NH2X

CO

2R'2NH

R'2NH2X

Ozawa, F.; Sugimoto, T.; Yuasa, Y.; Santra, M.; Yamamoto, T.; Yamamoto, A. Organometallics 1984, 3, 683.

35

R Br R

O

OH

O

R

O

OH+

Co2(CO)8, CO, base

3.6~5.0 MPa, 80 oC

R = Me 85% 10%

R = Ph 80% 7%

Ar-X ArCOCOOHCo2(CO)8

Me2SO4

Francalanci, F. ; Bencini, E.; Gardano, A.; Vincenti, M.; Foà, M. J. Organomet. Chem. 1986, 301, C27.

3636

Content

1. Introduction




5. Conclusion

Background


Hydroformylation


3737

Conclusion

Atom economical

Variety, wide application in industry and lab synthesis

Ni, Pd, Pt, Co, Rh catalysts, etc

Various influencing factors: substrate, catalyst, solvent, pressure,

temperature, additive, etc

3838

Acknowledgment

Thanks for Prof. Yu.

Thanks for my group members.

Thanks for all the teachers and the students.

39

Note

39

NR

R'

NR'R

Co(CO)4

Co(CO)4-

(OC)3CoNR'

R

CO

Co(CO)4-

(OC)4CoNR'

O

R

N

R'

O RCo(CO)4-

Co2(CO)8

CO

R = alkyl

NR'

Co(CO)4

Co(CO)4-

NR'

Co(CO)4

Co(CO)4-

4040

X PdXLnPdXLn

O

OPdXLn

OPdXLn

O ONu

O

PdLn CO

NuCO

cyclicacylmetalation

I

OSiR3 OSiR3

OCOOMe

75 %, trans/cis = 3:1

PdCl2(PPh3)2, MeOH

15 bar CO, 100 oC

4141

[Rh]

[Rh] Ar

[Rh] Ar

O

[Rh]

R

R

O Ar

R R

ArOO

[Rh]

O

RR

O[Rh]Ar

O

RR

OAr

ArB(OH)2

CO

R

R

CO

H+

R

R

B(OH)2

R'

O

R'

RR

O

[Rh(cod)Cl]2 20 atm CO

toluene80 oC,16 h

+

4242

MeR

Rh

MeR

CORh

OMe

R

RhO

MeR

O

MeR

O

MeMeR

CO, Rh(I)

oxidative addition

CO insertion

isomerization reductiveelimination

-carbonelimination

1

23

4

52

Me

BnO

O

MeMe

BnOCO+

5 mol% [Rh(cod)Cl]2 10 mol% DPPP

p-xylene130 oC, 2.5 h

(1 atm)

84 %

Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe...

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