Stereoselective Formation of Fully Substituted Ketone Enolates

Stereoselective Formation of Fully Substituted Ketone Enolates
Elvira Haimov, Zackaria Nairoukh, Alexander Shterenberg, Tiran Berkovitz, Timothy F. Jamison, and Ilan Marek

The application of stereochemically defined acyclic fully substituted enolates of ketones to the enantioselective synthesis of quaternary carbon stereocenters would be highly valuable. Herein, we describe an approach leading to the formation of several new stereogenic centers through a combined metalation–addition of a carbonyl–carbamoyl transfer to reveal in situ stereodefined α,α-disubstituted enolates of ketone as a single stereoisomer. This approach could produce a series of aldol and Mannich products from enol carbamate with excellent diastereomeric ratios.
The application of stereochemically defined acyclic fully substituted enolates of ketones to the enantioselective
synthesis of quaternary carbon stereocenters would be highly
valuable.Herein, we describe an approach leading to the
formation of several new stereogenic centers through acom-
bined metalation–addition of acarbonyl–carbamoyl transfer to
reveal in situ stereodefined a,a-disubstituted enolates of ketone
as asingle stereoisomer.This approach could produce aseries
of aldol and Mannich products from enol carbamate with
excellent diastereomeric ratiosv
The application of stereochemically defined acyclic
fully substituted enolates of ketones to the enantioselective
synthesis of quaternary carbon stereocenters would be highly
valuable.Herein, we describe an approach leading to the
formation of several new stereogenic centers through acom-
bined metalation–addition of acarbonyl–carbamoyl transfer to
reveal in situ stereodefined a,a-disubstituted enolates of ketone
as asingle stereoisomer.This approach could produce aseries
of aldol and Mannich products from enol carbamate with
excellent diastereomeric ratios

This paper was published in Angewandte Chemie International Edition (Angew. Chem. Int. Ed. 2016, 55, 5517 –5520) and selected as very important paper.

http://onlinelibrary.wiley.com/doi/10.1002/anie.201601883/full