CC BY-ND-NC 4.0 · Synthesis 2019; 51(01): 296-302
DOI: 10.1055/s-0037-1610381
paper
Copyright with the author

Diastereoselectivities in Reductions of α-Alkoxy Ketones Are Not Always Correlated to Chelation-Induced Rate Acceleration

,
Alana L. Hornstein
,
Annie Y. Zhao
,
Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, USA   Email: kwoerpel@nyu.edu
› Author Affiliations
Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support of this research (57206-ND1). The Shared Instrumentation Facility in the Department of Chemistry was constructed through the support of the National Center for Research Resources, National Institutes of Health, under Research Facilities Improvement Award Number C06 RR-16572-01. The cryogenic probe for the 600 MHz NMR was acquired through the support of the National Institute of Health S10 grant under Award Number OD016343.
Further Information

Publication History

Received: 15 October 2018

Accepted: 18 October 2018

Publication Date:
08 November 2018 (eFirst)

Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

The chelation-control model is used to predict stereochemical outcomes of many organometallic reactions. Diastereoselectivity arises due to reaction with a chelated intermediate with sterically differentiated faces. Earlier studies with dimethylmagnesium established that the chelated intermediate is a minor component of the reaction mixture, so reaction with the chelated intermediate must be faster than reaction with a non-chelated intermediate. High diastereoselectivity and chelation-induced rate acceleration are correlated with some hydride reducing agents. There are examples in which diastereoselectivity is high, but chelation-induced rate acceleration is not observed, however. In other cases, chelation-induced rate acceleration is observed, but diastereoselectivity remains low. These experiments illustrate that a revision to the chelation-control model is needed.

Supporting Information

 
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