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

Nicole D. Bartolo; Alana L. Hornstein; Annie Y. Zhao; K. A. Woerpel

doi:10.1055/s-0037-1610381

Synthesis, Table of Contents

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

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

Nicole D. Bartolo

,

Alana L. Hornstein

,

Annie Y. Zhao

,

K. A. Woerpel *

Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, USA Email: kwoerpel@nyu.edu

› Author Affiliations

Abstract

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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.

Key words

hydride reductions - chelation control - stereoselectivity

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References

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