Vsevolod Peshkov

Wipf Group Current Literature

10/12/2013

Diaminophosphine Oxide Ligand Enabled Asymmetric Nickel-Catalyzed Hydrocarbamoylations of Alkenes

Pavel A. Donets and Nicolai Cramer*

Laboratory of Asymmetric Catalysis and Synthesis, Institute of Chemical

Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne

(EPFL), Lausanne, Switzerland

J. Am. Chem. Soc. 2013, 135, 11772

Vsevolod Peshkov @ Wipf Group Page 1 of 14 11/9/2013

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The secondary phosphine oxide (SPO) concept:

For review on SPO, see: Ackermann, L. Synthesis 2006, 1557

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SPO early/late heterobimetallic intermediates in catalysis

Ackermann, L.; Born, R.; Spatz, J. H.; Meyer, D. Angew. Chem., Int. Ed. 2005, 44, 7216

Ackermann, L.; Althammer, A. Chem. Unserer Zeit 2009, 43, 74

Jin, Z.; Li, Y.-J.; Ma, Y.-Q.; Qiu, L.-L.; Fang, J.-X. Chem.—Eur. J. 2012, 18, 446

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Hydrocarbamoylation of Unsaturated Bonds;a Background

Nakao, Y.; Idei, H.; Kanyiva, K. S.; Hiyama, T. J. Am. Chem. Soc. 2009, 131, 5070

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Hydrocarbamoylation of Unsaturated Bonds;a Background

Nakao, Y.; Idei, H.; Kanyiva, K. S.; Hiyama, T.

J. Am. Chem. Soc. 2009, 131, 5070

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Optimization of Asymmetric Hydrocarbamoylation

68:3214L9

52:4810L8

72:2826L7

60:4041L6

-3L5

51:4910L4

-2L3

-5L2

57:4350L1

eeYieldLigand

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Optimization of Asymmetric

Hydrocarbamoylation

14:868710 mol%10 mol%

61:3918-10 mol%

eeYieldPPh3

SPO1

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SPO Preparation

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Optimization of Asymmetric

Hydrocarbamoylation

96.5:3.561SPO50.25

96.5:3.590SPO50.5

96.5:3.588SPO510

40:6082SPO410

84:1683SPO310

62:3840SPO210

eeYieldSPOx

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Scope of Asymmetric Hydrocarbamoylation

with SPO1

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Matched/Mismatched Stereocontrolwith Chiral Substrate 1p

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RP

H

R O

RP

R OH

RP

R O AlMe2AlMe3

- CH4

[Ni(COD)2]PPh3

RP

R O AlMe2

[Ni]

N H

O

Bn

N [Ni]

O

Bn PN

OAl

N

H

*

N

OBn H

N [Ni]

O

Bn P N

OAl

N*

HN [Ni]

O

Bn PN

OAl

N*

H

1a2a

Mechanistic Proposal of the Bimetallic Activation with SPO Ligands

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Catalytic Performance of the Preformed Lewis

Acid/Ligand SPO5-Al

1a 2a

N

PN

OH

tBu

tBu

Np

Np

1-

1-

nBuLi

NP

NOLi

tBu

tBu

Np

Np

1-

1-

ClAlMe2

N

PN

OAlMe2

tBu

tBu

Np

Np

1-

1-

SPO5-Al

N H

O

Bn[Ni(COD)2] 0.25 mol%

SPO5-Al 0.25 mol%N

OBn H

96 %, 97:3 ertoluene, 40 °C

No PPh3, No AlMe3

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CONCLUSIONS

• Application of SPO in the process involving

C-H activation

• New family of chiral SPO’s prepared and

utilized

• Possible further directions:

- Better understanding of PPh3 role

- Expanding of substrate scope to the use of

longer chains, internal double-bounds and different

carbonyl functionalities

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