title: Stereoselective Formation of Fully Substituted Ketone Enolates.
abstract: 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.
authors.affiliation: The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa, 3200009, Israel.
authors.forename: Elvira
authors.initials: E
authors.lastname: Haimov
authors.affiliation: The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa, 3200009, Israel.
authors.forename: Zackaria
authors.initials: Z
authors.lastname: Nairoukh
authors.affiliation: The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa, 3200009, Israel.
authors.forename: Alexander
authors.initials: A
authors.lastname: Shterenberg
authors.affiliation: The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa, 3200009, Israel.
authors.forename: Tiran
authors.initials: T
authors.lastname: Berkovitz
authors.affiliation: Massachusetts Institute of Technology, Department of Chemistry, 77 Massachusetts Ave., Bldg 18-590, Cambridge, MA, 02139, USA.
authors.forename: Timothy F
authors.initials: TF
authors.lastname: Jamison
authors.affiliation: The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa, 3200009, Israel. chilanm@tx.technion.ac.il.
authors.forename: Ilan
authors.identifier: 0000-0001-9154-2320
authors.initials: I
authors.lastname: Marek
keywords: carbamoyl transfer; enol carbamates; enolates; ketones; quaternary carbon stereocenters