Breaking Conjugation: Unusual Regioselectivity with 2-Substituted Allylic Substrates in the Tsuji-Trost Reaction.

ABSTRACT: η³-Allyl palladium complexes are key intermediates in Tsuji-Trost allylic substitution reactions. It is well known that (η³-1-aryl-3-alkyl substituted allyl)Pd intermediates result in nucleophilic attack at the alkyl substituted terminus. In contrast, the chemistry of (η³-1,2,3-trisubstituted allyl)Pd intermediates is relatively unexplored. Herein we probe the regioselectivity with 1,2,3-trisubstituted allylic substrates in Tsuji-Trost allylic substitution reactions. DFT investigation of cationic (η³-1-Ph-2-B(pin)-3-alkyl-allyl)Pd(PPh₃)₂ intermediates predict that nucleophilic attack should occur preferentially on anti-allyls rather than the syn-isomers to generate benzylic substitution products under Curtin-Ha

SUBMITTER: Kim BS 

PROVIDER: S-EPMC4045119 | biostudies-literature | 2014 Mar

REPOSITORIES: biostudies-literature