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- Title
Regio‐ and Diastereoselective Rhodium‐Catalyzed Allylic Substitution with Unstabilized Benzyl Nucleophiles.
- Authors
Pal, Debasis; Wright, Timothy B.; O'Connor, Ryan; Evans, P. Andrew
- Abstract
We have developed a highly regio‐ and diastereoselective rhodium‐catalyzed allylic substitution of challenging alkyl‐substituted secondary 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 a regio‐ and diastereoselective allylic substitution in the absence of an exogenous ligand. This reaction tolerates electronically diverse benzylzinc nucleophiles and an array of functionalized and/or challenging aliphatic 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.
- Subjects
NUCLEOPHILES; BENZYL halides; RHODIUM compounds; RHODIUM; ELECTROPHILES
- Publication
Angewandte Chemie, 2021, Vol 133, Issue 6, p3024
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202008071