Stereospecific Overman Rearrangement of Substituted Cyclic Vinyl Bromides: Access to Fully Substituted α-Amino Ketones

Creators: Velasco-Rubio, Álvaro; Alexy, Eric J.; Yoritate, Makoto; Wright, Austin C.; Stoltz, Brian M.

Abstract

A versatile thermal Overman rearrangement of enantioenriched, cyclic allylic alcohols providing tertiary allylic amines has been developed. The vinyl bromide used to control enantioselectivity in a preceding CBS reduction is utilized as a synthetic handle for the preparation of tertiary α-amino ketones and related derivatives in an asymmetric fashion.

Additional Information

© 2019 American Chemical Society. Received: September 21, 2019; Published: October 30, 2019. We thank NIH-NIGMS (R01GM080269) and Caltech for financial support. A.V.-R. thanks Xunta de Galicia for a predoctoral fellowship (ED481A-2018/34, 2018-2021). E.J.A. thanks the National Science Foundation for a predoctoral fellowship. We thank Dr. David VanderVelde (Caltech) for NMR expertise. Larry Henling (Caltech) and Dr. Michael Takase (Caltech) are thanked for X-ray crystallographic structure determination. Dr. Scott Virgil (Caltech) is thanked for instrumentation and SFC assistance. Accession Codes: CCDC 1955048 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. The authors declare no competing financial interest. This manuscript is dedicated to Professor Larry E. Overman (UC Irvine) for being an inspirational force in organic synthetic chemistry.

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