Loughborough University
Browse

Developing a methodology for catalytic asymmetric crotylation of aldehydes

Download (1.19 MB)
journal contribution
posted on 2021-01-25, 13:51 authored by Aleksandr E Rubtsov, Andrei MalkovAndrei Malkov
Asymmetric crotylation has firmly earned a place among the set of valuable synthetic tools for stereoselective construction of carbon skeletons. For a long time the field was heavily dominated by reagents bearing stoichiometric chiral auxiliaries, but now catalytic methods are gradually taking center stage, and the area continues to develop rapidly. This account focuses primarily on preformed organometallic reagents based on silicon and, to some extent, boron. It narrates our endeavors to design new and efficient chiral Lewis base catalysts for the asymmetric addition of crotyl(trichloro)silanes to aldehydes. It also covers the development of a novel protocol for kinetic resolution of racemic secondary allylboronates to give enantio- and diastereomerically enriched linear homoallylic alcohols. As a separate topic, cross-crotylation of aldehydes by using enantiopure branched homoallylic alcohols as a source of crotyl groups is discussed. Finally, the synthetic credentials of the developed methodology are illustrated by total syntheses of marine natural products, in which crotylation plays a key role in setting up stereogenic centers.

Funding

Russian Science Foundation grant 18-73- 10156

History

School

  • Science

Department

  • Chemistry

Published in

Synlett

Volume

32

Issue

14

Pages

1397-1405

Publisher

Thieme Publishing

Version

  • AM (Accepted Manuscript)

Rights holder

© Thieme

Publisher statement

This paper was accepted for publication in the journal Synlett and the definitive published version is available at https://doi.org/10.1055/s-0040-1706659.

Acceptance date

2020-12-09

Publication date

2021-01-18

Copyright date

2021

ISSN

0936-5214

eISSN

1437-2096

Language

  • en

Depositor

Prof Andrei Malkov. Deposit date: 20 January 2021

Usage metrics

    Loughborough Publications

    Exports

    RefWorks
    BibTeX
    Ref. manager
    Endnote
    DataCite
    NLM
    DC