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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
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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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