Vinyl epoxides are versatile precusors to highly functionalized compounds.¹ The combination of olefin and epoxide affords not only unique reactivity that cannot be harnessed from each moiety alone but also effective properties of the two functional groups. Because of the high utility of vinyl epoxide, various synthetic methods and strategies have been studied and applied to total synthesis of natural products. Nevertheless, enantioselective synthesis of vinyl epoxide is challenging and typically depends on enantioselective epoxidations of a few types of substrate. Kinetic resolution can be employed as an alternative strategy when there is no general, enantioselective synthetic method. Kinetic resolution has been successfully utilized for the synthesis of highly enantioenriched vinyl epoxide intermediates in total syntheses of chlorosulfolipids.² Because Denmark’s catalyst had provided good selectivity in kinetic resolution of dichlorinated cis-vinyl epoxide, a broad range of epoxides containing an electron withdrawing substituent are systematically examined under Denmark’s Lewis base-catalyzed enantioselective chlorinolysis conditions.³

References

1. He, J.; Ling J.; Chiu, P. Chem. Rev. 2014, 114, 8037–3128.
2. (a) Chung, W.-j.; Carlson, J. S.; Vanderwal, C. D. J. Org. Chem. 2014, 79, 2226–2241.(b) Chung, W.-j.; Carlson, J. S.; Bedke, D. K.; Vanderwal, C. D. Angew. Chem. Int. Ed. 2013, 52, 10052–10055.
3. (a) Denmark, S. E.; Barsanti, P. A.; Beutner, G. L.; Wilson, T. W. Adv. Synth. Catal. 2007, 349, 567–582. (b)Denmark, S. E.; Barsnati, P. A.; Wong, K.-T.; Stavenger, R. A. J. Org. Chem. 1998, 8, 2428–2429.