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. 2010 Mar 17;132(10):3295-7.
doi: 10.1021/ja1004703.

Asymmetric hydrovinylation of unactivated linear 1,3-dienes

Rakesh K Sharma  1 , T V RajanBabu
Affiliations

Asymmetric hydrovinylation of unactivated linear 1,3-dienes

Rakesh K Sharma et al. J Am Chem Soc. .

Abstract

Monosubstituted acyclic (E)-1,3-dienes undergo efficient hydrovinylation giving (Z)-3-alkylhexa-1,4-dienes upon treatment with catalytic amounts of bidentate phosphine-CoCl(2) complexes {[P~P](CoCl(2))} and Me(3)Al in an atmosphere of ethylene. The regioselectivity of the reaction (i.e., 1,4- or 1,2-addition) depends on the nature of the ligand and temperature at which the reaction is carried out. Complexes derived from (RR)-DIOP and (SS)-BDDP at -45 degrees C give very high enantioselectivities for several prototypical 1,3-dienes. In sharp contrast to the corresponding Ni(II)-catalyzed hydrovinylation, 1-aryl-substituted 1,3-dienes give almost exclusively achiral linear 1,4-addition products, unless the 2-position is also substituted. Solid-state structures of the precatalysts are presented.

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Figures

Figure 1
Figure 1
Solid-state structures of Precatalysts (RR)-[DIOP]CoCl2 and (SS)-[BDPP]CoCl2
Scheme 1
Scheme 1
A Possible Mechanism of Co(II)-Catalyzed Hydrovinylation of 1,3-Dienes
See this image and copyright information in PMC

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