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Regio‐ and Diastereoselective Rhodium‐Catalyzed Allylic Substitution with Unstabilized Benzyl Nucleophiles
Author(s) -
Pal Debasis,
Wright Timothy B.,
O'Connor Ryan,
Evans P. Andrew
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202008071
Subject(s) - allylic rearrangement , stereocenter , chemistry , rhodium , electrophile , nucleophile , substitution reaction , combinatorial chemistry , catalysis , medicinal chemistry , enantioselective synthesis , organic chemistry
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.