Developing a methodology for catalytic asymmetric crotylation of aldehydes
journal contributionposted 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.
Russian Science Foundation grant 18-73- 10156
- AM (Accepted Manuscript)
Rights holder© Thieme
Publisher statementThis 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.