Contentold.chem.pku.edu.cn/page/organic/Seminar/2006-2/Liuhan.pdf · 10 19 Ni catalyzed asymmetric...

1

1

Asymmetric Hydrovinylation:A Systematic Investigation During the

Last Three Decades.

Han Liu2006. 12. 1

2

Content

Introduction of HVRBrief history of HVRNi catalyzed asymmetric HVRPd catalyzed asymmetric HVRCo catalyzed asymmetric HVRApplication of asymmetric HVR Summary and outlookAcknowledgement

2

3

Introduction

4

Introduction

The perfect combination of organic chemistry and chemical industry.

3

5

Introduction

…… the paucity of the methods for the stereoselective incorporation of abundantly available carbon feed-stocks such as CO, CO2, HCN, or simple olefins to prochiral substrates is one of the major limitations in this area.

RajanBabu, T. V. Chem. Rev. 2003, 103, 2845

6

Introduction

Wilke, G. Angew. Chem. Int. Ed. 1988, 27, 185

The stimulated helix structure of a chiral polymer.

4

7

Introduction

Ziegler catalyst

∗

∗ n isotacticpolymerization

Bretinger, H.; Furbach, F.; Martn, H. unpublished work

8

Introduction

Cl

MeMgBr 3 mol% CuBr 3.3 mol% Ligand

DCM -78 oC 4 h

OO P N

OMe

OMe

89% yield96% ee

Tissot-Croset, K.; Alexakis, A. Tetrahedron Lett. 2004, 45, 7375

Chiral Catalyst

Suitable conditionsHigh yield High ee

The most important target of asymmetric HVR.

5

9

Introduction

Catalyst

∗

or

Polyethylene or polystyrene

Challenges in Asymmetric HVR

HVR

Isomerization

Dimerization

Polymerization

10

Brief history of HVR

Nickel Effect Where as the reaction of ethylene and triethylaluminum under pressure at 100 oC yields trialkylalminum compounds having long alkyl chains, the presence of small amounts of nickel salts induces the formation of butene. The discovery of this "nickel effect" represents the starting point for the development of the Ziegler catalysts.

Fischer, K.; Jonas, K.; Misbach, P.; Stabba, R.; Wilke, G. Angew. Chem. Int. Ed. 1973, 12, 943Ziegler, K.; Holzkamp, E.; Breil, H.; Martin, H. Angew. Chem. 1955, 67, 541

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11


1000 atmRhCl3-3H2O or RuCl3-3H2O

For RhCl3-3H2O 0.3 g catalyst, 138 g product.For RuCl3-3H2O 2.0 g catalyst, 158 g product.

ClCOCH3

90% yield at 50 oC

65% yield C8 olefins

40% yield at 50 oC

Alderson, T.; Jenner, E. L.; Lindsey Jr., R. V. J. Am. Chem. Soc. 1965, 87, 5638

12


ReviewsRajanBabu, T. V.; Nomura, N.; Jin, J.; Radetich, B.; Park, H.; Nandi, M. Chem. Eur. J. 1999, 5, 1963Gooβen, L. J. Angew. Chem. Int. Ed. 2002, 41, 3775RajanBabu, T. V. Chem. Rev. 2003, 103, 2845RajanBabu, T. V. Comprehensive Asymmetric Catalysis, Springer-Verleg: New York Chapter 12

Ni catalyzed HVRKawata, N.; Maruya, K.; Mizoroki, T.; Ozaki, A. Bull. Chem. Soc. Jan. 1971, 44, 3217

Pd catalyzed HVRBarlow, M. G.; Bryant, M. J.; Haszeldine, R. N.; Mackie, A. G. J. Organomet. Chem. 1970, 21, 215

Co catalyzed HVRPu, L. S.; Yamamoto, A.; Ikeda, S. J. Am. Chem. Soc. 1968, 90, 7170

Ir catalyzed HVRBhalla, G.; Oxgaard, J.; Periana, R. A.; Goddard, W. A., III. Organometallics, 2005, 24, 5499Oxgaard, J.; Bhalla, G.; Periana, R. A.; Goddard, W. A., III. Organometallics, 2006, 25, 1618

Pt catalyzed HVRCucciolito M. E.; D' Amora, A; Vitagliano, A. Organometallics 2005, 24, 3359

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13


Professor Günther WilkeProfessor Gérard BuonoProfessor T. V. RajanBabuProfessor Guillermo MüllerProfessor Walter LeitnerProfessor Dieter VögtProfessor Qi-Lin Zhou

14

Ni catalyzed asymmetric HVR

NiH

NiR

R Ni

NiR

R∗

Ni

R

Ni

R∗

Ni

Ni H

Ni H

R'

R

R

β-H elimination

R∗

R

dissociation

coordination

insertion coordination

insertion

Muller, G.; Ordinas, J. I. J. Mol. Cat. A: Chemical 1997, 125, 97

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15


Bogdanovic, B.; Henc, B.; Meister, B.; Pauling, H.; Wilke, G.Angew. Chem. Int. Ed. 1972, 11, 1023

π-C3H5Ni(L)X-AlX3

70% ee

DCM0 oC

π-C3H5Ni(L)X-AlX3

DCM-40 oC

64% ee

OP

O

OP

O

16


OP

O

Bogdanovic B. Angew. Chem. Int. Ed. 1973, 12, 954

π-C3H5Ni(L)X-AlX3

DCM-97 oC

80.6% ee

9

17


Wilke, G. Angew. Chem. Int. Ed. 1988, 27, 185

OH

NH2

NMePBr2

PNMe

BrBr

(-)-(1R, 5S)-myrtenal

80 oC

neat

87% 4 daysn-pentane

84%

+

PN

13%

THF -10 oC

PNH

H

Azaphospholene

Wilke, G.; Monkiewicz, J.; Kuhn, H. U.S. Patent 4912274

18


Wilke, G.; Monkiewicz, J. Chem. Abstr. 1988, 109, 6735

Azaphospholene[{π-C3H5NiCl}2]/ Et3Al2Cl3

> 90% yield 95% ee

+

[(allyl)Ni-Cl]2, Et3Al2Cl3ethylene, -70 oC, DCMS/C = 86, P:Ni:Al = 1:1:1 35% yield 92% ee

Wilke, G.; Monkiewicz, J.; Kuhn, H. U.S. Patent 4912274

10

19


PN

PNH

H

High reactivity and excellent selectivity.Low catalyst loading.Sensitive to moisture and air.Sensitive to reactive functional group in the substrates.Excess Et3Al2Cl3 must be used.Complex structure.

NiCl

NiCl

20


CO2CH3

NH3 Cl

OH

CH3COOCHOTEA CHCl3

CO2CH3

NHCHO

OH

LiAlH4THF

NHCH3

OH

OH

3eq. Ph2PClBenzene

TEA

N

O

OPPh2

PPh2

Ph2P

(2S,3R)-threonine

From (S)-phenylalanine 21% ee

From (S)-valine 10% eeFrom (S)-phenylglycine 4% ee

From (S)-aspartic acid 28% eeFrom (S)-glutamic acid 19% ee

From (S)-alanine 17% ee

AMPP

Buono, G.; Siv, C.; Peiffer, G.; Triantaphylides, C. J. Org. Chem. 1985, 50, 1782

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21


Ni(COD)2-AlEt2Cl-AMPP1 : 6 : 1

0.46% mol

Quantitative yield40 oC 85% ee10 oC 91% ee

0 oC 93% ee-20 oC 93% ee-30 oC 93% ee

15 min

225 min

Buono, G.; Siv, C.; Peiffer, G.; Triantaphylides, C. J. Org. Chem. 1985, 50, 1782

22


NiX

XNi P = R3P Ni

X

PLewis acid

NiP

Y

Y- = Lewis acid-X complex

NiP

NiP

Y

H NiP

Y

Nomura, N.; Jin, J.; Park, H.; RajanBabu, T. V. J. Am. Chem. Soc. 1998, 120, 459RajanBabu, T. V.; Nomura, N.; Jin, J.; Nandi, M.; Park, H.; Sun, X. J. Org. Chem. 2003, 68, 8431

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23

Ni catalyzed asymmetric HVRH Ni

P

Y Ar

NiP

YH

Ar

NiP

Y∗Ar

∗Ar

maybe an olefin complex

NiP

YAr∗

NiP

Y∗Ar

NiP

Y

Nomura, N.; Jin, J.; Park, H.; RajanBabu, T. V. J. Am. Chem. Soc. 1998, 120, 459RajanBabu, T. V.; Nomura, N.; Jin, J.; Nandi, M.; Park, H.; Sun, X. J. Org. Chem. 2003, 68, 8431

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MeO

C2H4, 0.70 mole% [(allyl)Ni-Br]2(R)-MOP-NaBAr4/DCM

Ar = 3,5-bis-CF3-C6H3MeO

-56 oC

>98% yield and 62% ee

OMePPh2

CH2CH3PPh2

13% yield and 3% ee

Nomura, N.; Jin, J.; Park, H.; RajanBabu, T. V. J. Am. Chem. Soc. 1998, 120, 459

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MeO

0.7mol% [(allyl)Ni-Br]2Ligand-NaBAr4/DCM

ethylene (1 atm) -70 oC MeOAr = 3,5-bis-CF3-C6H3

RPPh2

R = PPh2 0% yieldR = OMe >98% yield 62% eeR = OBn 97% yield 73% eeR = OPri 69% yield 70% eeR = Et 12% yield <3% eeR = OC(O)CH3 0% yieldR = P(O)Ph2 0% yield

OPPh2

Ph (R,R) 96% yield 71% ee(R,S) 79% yield 65% ee

Nandi, M.; Jin, J.; RajanBabu, T. V. J. Am. Chem. Soc. 1999, 121, 9899

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X

Br

HP(O)(OEt)2/Pd(OAc)2

dppb/ EtNPri/DMSO100 oC 12 h

X

P

X

P(O)(OEt)2

LAH/ether/3 hreflux

X

PH2

KH/THF/6 h

O

O2SO

X = H AgOTf and AgClO4 can be used.X = CH2OCH3 AgNTf2, AgSbF6, and NaBAr4 can be used.up to 50% ee

Nandi, M.; Jin, J.; RajanBabu, T. V. J. Am. Chem. Soc. 1999, 121, 9899

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27


CatalystscCO2 or DCM

NaBARF

PN

PNH

HNi

Ni

Cl

Cl

Wegner, A.; Leitner, W. Chem. Commun. 1999, 1583

Enantioselective excess of 3-phenyl-1-butene fromasymmetric HVR in CO2(ball) and DCM(square).

28


O OPN

X

X = MeO 7.6% ee (R)X = Cl 87.2% ee (S)

O OPN

X

X = MeO 56.4% ee (R)X = Cl trace product

O OPN

up to 94.8% ee (R)

Francio, G.; Faraone, F.; Leitner, W. J. Am. Chem. Soc. 2002, 124, 736Feringa, R. L. Acc. Chem. Res. 2000, 33, 346

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29


Holscher, M.; Francio, G.; Leitner, W. Organometallics 2004, 23, 5606

NiHD

LX

NiD

LH

X

NiD

LX

∗

NiD

L

XNi

L XD

∗

30


Holscher, M.; Francio, G.; Leitner, W. Organometallics 2004, 23, 5606

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31


OO OPh

RO

Ar2POBn

R = NHAc

OO OPh

RO

Ar2POBn

Ar = 3,5-(CH3)2-C6H3

Ar = 3,5-(CH3)2-C6H3 89% 89% 81% (S)

Ar = 3,5-(CF3)2-C6H3 42% >99% 62% (S)

R = CF3CONH 40% 40% 87% (S)

R = PhCONH 23% 23% 82% (S)

OO OPh

OMeNHAc

OAr2P

OO OPhO

Ar2P OBnRR = NHAc

Ar = 3,5-(CH3)2-C6H3 62% >99% 32% (S)

Ar = 3,5-(CF3)2-C6H3 35% >99% 28% (S)

Ar = 3,5-(CH3)2-C6H3 93% 96% 9% (S)

Ar = 3,5-(CF3)2-C6H3 93% >99% 45% (S)

Park, H.; RajanBabu, T. V. J. Am. Chem. Soc. 2002, 124, 734

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OTBS

F3C

CF3

O N

RajanBabu, T. V.; Nomura, N.; Jin, J.; Nandi, M.; Park, H.; Sun, X. J. Org. Chem. 2003, 68, 8431

The range of the substances cannot be expanded easily.

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33


[(allyl)Ni-Br]2, Cy3P

AgOTf, DCM, 2 h1 mol%, -70 oC

rac. >99% yield

[(allyl)Ni-Br]2, Ph3P

AgOTf, DCM, 2 h0.7 mol%, -55 oC

rac. 97% yield

Kumareswaran, R.; Nandi, M.; RajanBabu, T. V. Org. Lett. 2003, 5, 4345

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P = Ph3P


HNi

P

NiP

NiP

NiP HX

NiP

X

18

35


P = Cy3P


NiP HX Ni

P

X

NiP

NiP

36


[(allyl)Ni-Br]2, Ligand

NaBARF, DCM1.5 mol%, -65 to -50 oC

Ar = 3,5-(CF3)2-C6H3 99% yield80% ee

OO P N

Ph

Ph

(Ra, Sc, Sc)


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37


Br

O

H 1. (R,R)-butane-2,3-diol, H+

2. HP(O)(OEt)2/Pd(OAc)2dppb, EtNPri

2, DMSO3. LAH/THF

O

O

PH2 O O

O2S

R R

KH

P

O

O

R

R

P

O

O

R

RR = Me 91% ee (R)R = Et 88% ee (R)

P

O

O

71% ee (R)

P

O

O

85% ee (R)

P

O

O

85% ee (R)

P

O

O

90% ee (S)

Zhang, A.; RajanBabu, T. V. Org. Lett. 2004, 6, 1515

38


Bui

[(allyl)Ni-Br]2 0.00035 equiv.Ligand (R = Me) 0.0007 equiv.

NaBAr4 0.00073 equiv.DCM -55 oC 4 h

Bui

S/C = 1428conversion 86%

72% ee


P

O

O

R

R

20

39


OO OPhO

P OBnR

R = NHAc

OO OPh

RO OBn

R = NHAc

OO

POO

(R)-BINAPO2 95% yield 62% ee (S)

(S)-BINAPO2 26% yield 2% ee (R)

(R)-BINAPO2 84% yield 44% ee (S)(S)-BINAPO2 83% yield 19% ee (S)

OO OPh

ROBn

OPO O

R = NHAc

(R,R) 53% yield 5% ee (R)(S,S) 83% yield 30% ee (S)

The evidence of the hemilabile nature of these ligands.

Park, H.; Kumareswaran, R.; RajanBabu, T. V. Tetrahedron 2005, 61, 6352

Counterion: BARF and SbF6- are much better than OTf- and BF4

-

40


OCH2PhPPh2

AgSbF6 and AgNTf2 >99% yield 50% ee

OO P N

Ph

Ph

(Ra, Sc, Sc)

NaBARF >99% yield 80% eeAgSbF6 >99% yield 34% ee


21

41


OO P N

OO P N

Et Et

Et Et

OO P N

Ph

Ph

O

OPN

O

OPN


No product when these five ligands were used.

42


Me

OHOH

Me

H

HMe

pseudopterosin A-F aglycone

Zhang, A,; RajanBabu, T. V. J. Am. Chem. Soc. 2006, 128, 54

H

∗

∗

R H

XH

22

43


L1 >99% yield 85% ee (R)

L1 >99% yield 93% ee (R)

L2 >99% yield 96% ee (S)

L2 >99% yield >99% ee (S)

L1 >99% yield 38% ee (R)

L2 >99% yield 95% ee (S)O

O

O

P

OO P N

Ph

Ph

(Ra, Sc, Sc)

L2

L1

Zhang, A,; RajanBabu, T. V. J. Am. Chem. Soc. 2006, 128, 54

44


NH

NHN

OH

Me

O

Lyngbyatoxin A

R

ethylene 1 atm

[(allyl)Ni-Br]2, Ligand1 ~ 5 mol%

NaBARF, DCM, -70 oCR

OO P N

Ph

Ph

(Ra, Sc, Sc)

Zhang, A.; RajanBabu, T. V. J. Am. Chem. Soc. 2006, 128, 5620

23

45


Zhang, A.; RajanBabu, T. V. J. Am. Chem. Soc. 2006, 128, 5620

R

R = H >99% yield >95% eeR = Me >99% yield 90% eeR = Cl >90% yield 90% ee

>99% yield 93% ee

70% yield >95% ee60% yield >95% ee (24 oC)

46


[Ni(allyl)Br(ligand)]/NaBARFEthylene (1 atm) DCM

OO P

NPh

Ph

(Sa,R,R)

35 oC, 2.5 h

96% conversion84% selectivity99% ee

Shi, W.-J.; Zhang, Q.; Xie, J.-H.; Zhu, S.-F.; Hou, G.-H.; Zhou, Q.-L. J. Am. Chem. Soc. 2006, 128, 2780

24

47


R'

R = p-Me, m-Me, m-MeO, p-Cl, p-MeO

R

R' = i-Pr94% ~ 99% eeR = Ph, R' = Et, n-Pr, i-Bu70% ~ 88% ee

RR = i-Pr, c-C6H1199% ee

Shi, W.-J.; Zhang, Q.; Xie, J.-H.; Zhu, S.-F.; Hou, G.-H.; Zhou, Q.-L. J. Am. Chem. Soc. 2006, 128, 2780

48

Pd catalyzed asymmetric HVR

Pd P

Pd P

Pd P

Pd P

PdP

PdH

P

PdPHPd

Solv PPdP

Solv

H

Albert, J.; Caena, M.; Granell, J.; Muller, G.; Ordinas, J. I.; Panyella, D.; Puerta, C.; Sanudo, C.; Valerga, P. Organometallics 1999, 18, 3511

25

49


tBu POPh (-)-menth

tBu

POPh (+)-menth

tBu POPh (-)-menth

tBu

POPh (+)-menth

PO

OPh

(+)-menth

(-)-menth

PO

OPh

(+)-menth

(+)-menth

PO

OPh

(-)-menth

(-)-menth

86% ee S config.

83% ee R config.

37% ee S config.

29% ee R config.

none

42% ee R config.

38% ee S config.

Bayersdorfer, R.; Ganter, B.; Englert, U.; Keim, W.; Vogt, D. J. Organomet. Chem. 1998, 552, 187

The chirality of phosphorous atom dominates the enantioselectivity in the hydrovinylation of styrene.

50


[(η3-C4H7)Pd(cod)]BF4

PPh2SiMe3Cr

OCOC CO

49% yield92% ee

Englert,U.; Harter, R.; Vasen, D.; Salzer, A.; Eggeling, E.; Vogt, D. Organometallics, 1999, 18, 4390

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R R

PBz Bz

Ph

Li THF20 h

PBz Li

Phr. t.

CyBr

r. t.10 min

PBz Cy

PhNiCl2(PBzCyPh)2

NiCl2THF/EtOH

r. t. Stable to air and moisture.

NPd NiCl2(PBzCyPh)2

Cl

2 THF 45 minr. t.

NPd

R R

Cl

PBzCyPhPBzCyPh

Separated by silica gel column chromatography.

[Pd(µ−Cl)(η3-2-MeC3H4)]2

r. t. 45 min PdCl

The catalyst for HVR.Confirmed by XRD.

Albert, J.; Caena, M.; Granell, J.; Muller, G.;Ordinas, J. I.; Panyella, D.; Puerta, C.; Sanudo, C.; Valerga, P. Organometallics 1999, 18, 3511

Albert, J.; Bosque, R.; Cadena, J. M.; Delgado, S.; Graell, J.; Muller, G.; Ordinas, J. I.; Bardia, M. F.; Solans, X. Chem. Eur. J. 2002, 8, 2279

52


R-Catalyst 0.1% mol 15oC 62% conversion 60% ee

S-Catalyst 0.1% mol 15oC 62% conversion 59% ee(S)

S product

R product

(S)

R-Catalyst 0.1% mol 15oC 100% conversion 85% ee

S-Catalyst 0.1% mol 15oC 83% conversion 84% ee

S product

R product

Albert, J.; Caena, M.; Granell, J.; Muller, G.;Ordinas, J. I.; Panyella, D.; Puerta, C.; Sanudo, C.; Valerga, P. Organometallics 1999, 18, 3511

Albert, J.; Bosque, R.; Cadena, J. M.; Delgado, S.; Graell, J.; Muller, G.; Ordinas, J. I.; Bardia, M. F.; Solans, X. Chem. Eur. J. 2002, 8, 2279

27

53


OP

N

Ph

MeMe

H3B

PhLiR

-78 oC N

Ph

Me

HO

PPhR

H3B

Me

MeOH/H+P

RPhMeO

BH3 Amine PR

PhMeO

R = 1-naphthyl, 9-phenanthryl, o-biphenylyl

PR

PhMeO

BH3 LiR'-78 oC P

RR'Ph

BH3 Amine PR

R'Ph Amine P CH2SiPh3Ph

BH3

sec-LiBuPh3SiCl

P MePh

BH3

R' = CH3, i-C3H7, Ph3SiCH2

Grabulosa, A.; Muller, G.; Ordinas, J. I.; Mezzetti, A.; Maestro, M. A.; Font-Bardia, M.; Solans, X.; Organometallics 2005, 24, 4961

54


O

OMeO

OMe

O

< 5% conversion < 5% conversion ~ 0% conversion

P i-C3H7Ph

BH3

0.1% mol2 h 25 oC

Grabulosa, A.; Muller, G.; Ordinas, J. I.; Mezzetti, A.; Maestro, M. A.; Font-Bardia, M.; Solans, X.; Organometallics 2005, 24, 4961

OMe 46% conversion95.3% selectivity

45% ee74 TOF(h-1)

28

55


PPh RLiH2C

BH3

R =

R =SiMe

MeCl

Me

1CI

SiSi Si

Si

Si

Cl

Cl

Cl

Cl

2 CISiSi Si

Si

Si

Si

Si

Si SiCl Cl

SiSi

Si SiCl Cl

Si

Si

Si

Si

Cl

Cl

Cl

Cl

3 CI

Rodriguez, L.-I.; Rossell, O.; Seco, M.; Grabulosa, A.; Muller, G.; Rocamora, M. Organometallics, 2006, 25, 1368

56


SiSi Si

Si

Si

Si

Si

Si Si

SiSi

Si Si

Si

Si

Si

Si

0.2% mol

P

P

P P

P

P

P P

Pd-1P1 68% eePd-2P1 63% eePd-3P1 65% ee

BF4- as conterion

BARF as conterionPd-2P1 77% eePd-3P1 79% ee

Rodriguez, L.-I.; Rossell, O.; Seco, M.; Grabulosa, A.; Muller, G.; Rocamora, M. Organometallics, 2006, 25, 1368

29

57


OOP

NRR

R = Me 10% yield 17% eeR = i-Pr 44% yield 38% eeR = -(CH2)4- 5% yield 18% ee

OOP

N

OOP

N

OOP

ORO

OP

N

OOP

O

Ph

Ph

(R,R,R) 8% yield 24% ee(R,S,S) 49% yield 23% ee

(R,R) 29% yield 26% ee

(R,S) 23% yield 9% ee

R = Ph 30% yield 34% eeR = 2,6-Me2Ph 42% yield 33% ee

OMe

(R,R) trace product

(R,S) 22% yield 20% ee

OMe (R,R) 22% yield 36% ee(R,S) 31% yield 21% ee

Shi, W.-J.; Xie, J.-H.; Zhou, Q.-L. Tetrahedron: Asymmetry 2005, 16, 705

58


0.5% mol [Pd(C3H5)Cl] LigandNaBARF, Toluene, 1 bar, 25 oC

R R R

Shi, W.-J.; Xie, J.-H.; Zhou, Q.-L. Tetrahedron: Asymmetry 2005, 16, 705

R = H 50% yield 64% eeR = CH3 10% yield 92% ee

Higher conversion, lower selectivity, higher ee.

OOP

N

30

59

Co catalyzed asymmetric HVR

HCoL3C2H5CoL3

H(N2)CoL3

C2H5CoL3

C2H5C2H4CoL3

C2H5

HCoL3CoL3

C2H5

HCoL3

C4H8

L = PPh3

C4H8

C2H4

C2H4

Pu, L. S.; Yamamoto, A.; Ikeda, S. J. Am. Chem. Soc. 1968, 90, 7170

60


NN N

Ph2P PPh2 Ph2P PPh2 PPh2 PPh2

OPPh2 PPh2 PPh2 PPh2

MeO OMe

Grutters, M. M. P.; Muller, C.; Vogt, D. J. Am. Chem. Soc. 2006, 128, 7414

31

61


O

O PPh2

PPh2

P P

MeO

OMe

NH

NH

O

O

PPh2

PPh2

N

N

PPh2

PPh2

NH

NH

PPh2

PPh2

8% yield 14% ee (R) 30% yield 26% ee (R)

74% yield 47% ee (R) trace producttrace product

Grutters, M. M. P.; Muller, C.; Vogt, D. J. Am. Chem. Soc. 2006, 128, 7414

62

Application of HVR

Br

[(allyl)Ni(Ligand)]1 mol% 2 h

ethylene 1 atm98 % yield

>99% selectivityBr

89% ee

(dppp)NiCl21.6 mol%i-BuMgCl

Kumada Coupling

1. O3, MeOH, then Me2S2. KMnO4/acetone

COOH

(R)-ibuprofen

OO OPh

RO

Ar2POBn

R = NHAcAr = 3,5-(CH3)2-C6H3

Park, H.; Kumareswaran, R.; RajanBabu, T. V. Tetrahedron 2005, 61, 6352Park, H.; RajanBabu, T. V. J. Am. Chem. Soc. 2002, 124, 734

32

63

Application of HVR

Me

Me

(R)-(-)-curcumene

Me

Me

O

(S)-(+)-ar-tumerone

Me

Me

H

Me

erogorgiaene

O OH

Me

Me

HO

heliannuol A2

NOMe

HMe

Me

pseudopteroxazole

Some natural products containing chiral centers at benzylic positions.

64

Application of HVR


P

O

O

Me

[(allyl)Ni-Br]2/LigandDCM/NaBAr4

-55 oC 2 h S/C = 143Ar = 3,5-di-CF3-C6H3

Me>99% conversion>99% selectivityer = 93 : 7 by HPLC

1. 9-BBN (1.2 eqiv.)

2. Pd(PPh3)4 5% mol

THF 0 oC to r.t.

K3PO4, 60 oCBr

THF/dioxane 14 h

Me

Me

(R)-(-)-curcumene

55% overall yield3 steps

ethylene

33

65

Application of HVR


Me

1. disiamylborane

2. NaOH/H2O2, 0 oC to r.t.Me

OH

THF, 0 oC to r.t. Swern Oxidation

84%90%

Me

O

MgBrTHF, -78 oC to r.t.

78% Me

OH

Swern Oxidation

44% Me

Me

O

(S)-(+)-ar-tumerone26% overall yield

66

Summary

High reactivity.High selectivity of branched product.Excellent enantioselectivity.Norbornene, different dienes, and substituted styrenescan be good substrates.Low catalyst loading.Potential application in chemical industry.

34

67

Outlook

Improve the reactivity and selectivity when the range of substrates is expanded.Develop new hemilabile and tunable ligands for asymmetric HVR.Develop new recyclable catalysts.Develop Co and other transition metals catalyzed asymmetric HVR.

68

Acknowledgement

Professor Professor DuDu, , DaDa--MingMing

Professor Professor XuXu, , JiaJia--Xi and Professor Zhang, Xi and Professor Zhang, QiQi--HanHan

All of the professors in the institute of organic chemistry.All of the professors in the institute of organic chemistry.

All of the current and past members of our group.All of the current and past members of our group.

35

69

Appendix I

PPh2

OCH3

The first introduction of the concept of hemilabile ligands.

RuOOPP

Cl

ClRu

OPP

Cl

ClO CO

RuOPP

Cl

ClO

OC

Jeffrey, J. C.; Rauchfuss, T.B. Inorg. Chem. 1979, 18, 2658

P PPh

H3CO

OCH3

Ph

DIPAMP

Vineyard, B. D.; Knowles, W. S.; Sebacky, G. L.; Backman, G. L.; Weinkauff, D. J. J. Am. Chem. Soc. 1977, 99, 5946

70

Appendix II

Britovsek, G. J.; Cavell, K. J.; Keim, W. J. Mol. Cat. A: Chemical 1996, 110, 77

PdP

O OEt

Ph Ph

BF4Pd Pd

N

O O

BF4 BF4

N

O OCH3

PdS

O OEt

Ph

BF4 PdN

O

Ph

BF4

36

71

Appendix III

COOH1. ClCOOEt, TEA2. tert-leucinol3. SOCl2

N

O

54%Me

Li

THF, -78 oC

N

O

Me

1. 1.8 M H2SO4

2. LiAlH4OH

Me66%

dppe, Br2 Br

Me97% Li

THF

Me

(S)-(+)-curcumene90%

Meyers, A. I.; Stoianova, D. J. Org. Chem. 1997, 62, 5219-5221

72

Appendix IV

Me

O(EtO)2POCH2COOEt

NaH, THF86%

Me

COOEt DIBAL-HTHF90%

Me

OH baker's yeast5d, 21%

Me

OH TsCl, PyNaI, acetone

65%

Me

I THF, CuI

77%MgBr

Me(S)-(+)-curcumene

Fuganti, C.; Serra, S.; Dulio, A J. Chem. Soc., Perkin Trans. 1, 1999, 279-282

37

73

Appendix V

Ru

R'H

R''

Cy3POC

Cl

RuCy3P

OCCl

R'R''

RuCy3P

OCCl

R'R''

H

RuCy3P

OCCl

HR''

R'

R'

R''

R''R'

Yi, C. S.; Lee, D. W.; Chen, Y. Organometallics 1999, 18, 2043

74

Appendix VI

IrN

Oxgaard, J.; Bhalla, G.; Periana, R. A.; Goddard, W. A., III. Organometallics, 2006, 25, 1618Bhalla, G.; Oxgaard, J.; Periana, R. A.; Goddard, W. A., III. Organometallics, 2005, 24, 5499

M

MM H

38

75

Appendix VII

N

P

P

Pt

PhPh

PhPh

2+

N

P

P

Pt

PhPh

PhPhR

Me Me

Me

N

P

P

Pt

PhPh

PhPh

MeMeMe

RH

N

P

P

Pt

PhPh

PhPh

MeMeMe

RH

N

P

P

Pt

PhPh

PhPh

2+Me

MeMe

R

MeMeMe

R

Me

MeR

Me

Cucciolito M. E.; D' Amora, A; Vitagliano, A. Organometallics 2005, 24, 3359

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