BINAP-CuH-catalysed enantioselective allylation using alkoxyallenes to access 1,2-syn-tert,sec-diols

Abstract

Herein, we present an economical method for highly enantioselective and diastereoselective Cu-BINAP-catalysed reductive coupling of alkoxyallenes with a range of electronically and structurally diverse ketones to afford 1,2-syn-tert,sec-diols, using PMHS as the hydride source. This reductive coupling has also been efficiently employed in the enantioselective desymmetrization of prochiral cyclic ketones harboring quaternary centres, in high yields with exclusive diastereoselectivity. Density Functional Theory (DFT) calculations are used to elucidate that the reaction is facilitated by a kinetically favourable “open” Z-enolate copper–alkoxyallene conformer, occurring at a lower Gibbs free energy barrier (by 3.9 kcal mol−1) than its E-enolate counterpart, dictating the stereoselectivity. Subsequently, this Z-enolate conformer synchronizes with appropriate nucleophilic faces to achieve the targeted syn-diastereoselectivity in the product through six-membered chair-like transition states during ketone addition.

Graphical abstract: BINAP-CuH-catalysed enantioselective allylation using alkoxyallenes to access 1,2-syn-tert,sec-diols

Supplementary files

Transparent peer review

To support increased transparency, we offer authors the option to publish the peer review history alongside their article.

View this article’s peer review history

Article information

Article type
Edge Article
Submitted
15 Oct 2024
Accepted
04 Nov 2024
First published
21 Nov 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024, Advance Article

BINAP-CuH-catalysed enantioselective allylation using alkoxyallenes to access 1,2-syn-tert,sec-diols

N. Navaneetha, S. Maurya, P. Behera, S. B. Jadhav, L. R. Magham, J. B. Nanubolu, L. Roy and R. Chegondi, Chem. Sci., 2024, Advance Article , DOI: 10.1039/D4SC07002J

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements