Asymmetric Remote C–H Functionalization: Use of Internal Olefins in Tandem Hydrometallation–Isomerization–Asymmetric Conjugate Addition Sequences*
Laura Mola A , Mireia Sidera A and Stephen P. Fletcher A B
+ Author Affiliations
- Author Affiliations
A Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK.
B Corresponding author. Email: stephen.fletcher@chem.ox.ac.uk
Australian Journal of Chemistry 68(3) 401-403 https://doi.org/10.1071/CH14556
Submitted: 11 September 2014 Accepted: 15 October 2014 Published: 21 November 2014
Abstract
We describe catalytic asymmetric C–C formation using terminal alkyl-metal nucleophiles generated from internal olefins through a ‘chain-walking’ isomerization mechanism. Hydrometallation of internal olefins with the Schwartz reagent gives the least hindered alkyl-zirconocene after thermal (60°C in THF) isomerization. After switching the solvent from THF to dichloromethane, the alkyl-zirconocenes can be used in copper-catalyzed asymmetric conjugate additions. Addition to a variety of cyclic α,β-unsaturated species were achieved in modest (22–50 %) yield with high (84–92 % ee) enantioselectivity. This work demonstrates that remote C–H functionalization coupled with asymmetric C–C bond formation is possible, but the present procedures are limited in terms of yield and olefin scope.
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