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Catalytic S N 2′‐ and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis
Author(s) -
Shi Ying,
Hoveyda Amir H.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201600309
Subject(s) - enantioselective synthesis , allylic rearrangement , catalysis , chemistry , reagent , enantiomer , yield (engineering) , combinatorial chemistry , selectivity , substitution (logic) , carbene , natural product , enantiomeric excess , organic chemistry , stereochemistry , medicinal chemistry , materials science , metallurgy , computer science , programming language
A catalytic method for the site‐ and enantioselective addition of commercially available di‐B(pin)‐methane to allylic phosphates is introduced (pin=pinacolato). Transformations may be facilitated by an NHC–Cu complex (NHC=N‐heterocyclic carbene) and products obtained in 63–95 % yield, 88:12 to >98:2 S N 2′/S N 2 selectivity, and 85:15–99:1 enantiomeric ratio. The utility of the approach, entailing the involvement of different catalytic cross‐coupling processes, is highlighted by its application to the formal synthesis of the cytotoxic natural product rhopaloic acid A.