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. 2008 Sep 5;73(17):6772-9.
doi: 10.1021/jo801098z. Epub 2008 Aug 6.

Enantioselective intramolecular hydroarylation of alkenes via directed C-H bond activation

Hitoshi Harada  1 , Reema K Thalji, Robert G Bergman, Jonathan A Ellman
Affiliations

Enantioselective intramolecular hydroarylation of alkenes via directed C-H bond activation

Hitoshi Harada et al. J Org Chem. .

Abstract

Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe)2]2 and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer.

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Figures

Figure 1
Figure 1
Absolute configuration determined by X-ray structure obtained of sulfinyl imine (Ss,R)-33
Figure 2
Figure 2
Absolute configuration determined by X-ray structure obtained hydrazone (2R,3R)-34
Scheme 1
Scheme 1
Chart 1
Chart 1
Chiral Monodentate Phosphorus Ligands
See this image and copyright information in PMC

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