Regio‐ and Diastereoselective Rhodium‐Catalyzed Allylic Substitution with Unstabilized Benzyl Nucleophiles
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Authors
Pal, Debasis
Wright, Timothy B
O'Connor, Ryan
Evans, P. Andrew
Date
2020-08-24
Type
journal article
Language
en
Keyword
Allylic Substitution , Benzylzinc Nucleophile , Hard Nucleophile , Regio- and Diastereoselective , Rhodium(III) Chloride
Alternative Title
Abstract
We have developed a highly regio‐ and diastereoselective rhodium‐catalyzed allylic substitution of challenging alkyl‐substituted branched allylic carbonates with benzylzinc reagents, which are prepared from widely available benzyl halides. This process utilizes rhodium(III) chloride as a commercially available, high‐oxidation state and bench‐stable pre‐catalyst to provide a rare example of regio‐ and diastereoselective allylic substitution in the absence of an exogenous ligand. This reaction tolerates both electronically diverse benzylzinc nucleophiles and an array of functionalized and/or challenging aliphatic secondary allylic electrophiles. Finally, the configurational fluxionality of the rhodium‐allyl intermediate is exploited to develop a novel diastereoselective process for the construction of vicinal acyclic ternary/ternary stereogenic centers, in addition to a cyclic ternary/quaternary derivative.
Description
This is the peer reviewed version of the following article: Pal, D., Wright, T..B., O’Connor, R. and Evans, P.A. (2020), Regio‐ and Diastereoselective Rhodium‐Catalyzed Allylic Substitution with Unstabilized Benzyl Nucleophiles. Angew. Chem. Int. Ed.. Accepted Author Manuscript. doi:10.1002/anie.202008071, which has been published in final form at https://doi.org/10.1002/anie.202008071. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
Citation
Pal, D., Wright, T..B., O’Connor, R. and Evans, P.A. (2020), Regio‐ and Diastereoselective Rhodium‐Catalyzed Allylic Substitution with Unstabilized Benzyl Nucleophiles. Angew. Chem. Int. Ed.. Accepted Author Manuscript. doi:10.1002/anie.202008071
Publisher
Wiley