Premium
Stereoselective Synthesis of Trisubstituted Alkenes through Sequential Iron‐Catalyzed Reductive anti ‐Carbozincation of Terminal Alkynes and Base‐Metal‐Catalyzed Negishi Cross‐Coupling
Author(s) -
Cheung Chi Wai,
Hu Xile
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201504049
Subject(s) - stereoselectivity , chemistry , electrophile , catalysis , aryl , combinatorial chemistry , substrate (aquarium) , reagent , alkyl , negishi coupling , alkyne , coupling reaction , regioselectivity , organic chemistry , oceanography , geology
The stereoselective synthesis of trisubstituted alkenes is challenging. Here, we show that an iron‐catalyzed anti ‐selective carbozincation of terminal alkynes can be combined with a base‐metal‐catalyzed cross‐coupling to prepare trisubstituted alkenes in a one‐pot reaction and with high regio‐ and stereocontrol. Cu‐, Ni‐, and Co‐based catalytic systems are developed for the coupling of sp‐, sp 2 ‐, and sp 3 ‐hybridized carbon electrophiles, respectively. The method encompasses a large substrate scope, as various alkynyl, aryl, alkenyl, acyl, and alkyl halides are suitable coupling partners. Compared with conventional carbometalation reactions of alkynes, the current method avoids pre‐made organometallic reagents and has a distinct stereoselectivity.