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Enantioselective Synthesis of Multisubstituted Allenes by Cooperative Cu/Pd‐Catalyzed 1,4‐Arylboration of 1,3‐Enynes
Author(s) -
Liao Yang,
Yin Xuemei,
Wang Xihong,
Yu Wangzhi,
Fang Dongmei,
Hu Lianrui,
Wang Min,
Liao Jian
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201912703
Subject(s) - enantioselective synthesis , transmetalation , catalysis , chemistry , yield (engineering) , phosphine , sulfoxide , combinatorial chemistry , limiting , stereochemistry , organic chemistry , medicinal chemistry , materials science , mechanical engineering , engineering , metallurgy
A cooperative Cu/Pd‐catalyzed enantioselective synthesis of multisubstituted allenes is established. By employing chiral sulfoxide phosphine (SOP)/Cu and PdCl 2 (dppf) complexes as catalysts, the 1,4‐arylboration of 1,3‐enynes provides an efficient approach to trisubstituted chiral allenes with up to 92 % yield and 97:3 er. Furthermore, by using 2‐substituted 1,3‐enynes as substrates, the tetrasubstituted chiral allenes were successfully generated using this strategy. Finally, theoretical calculations indicate that the transmetallation of the allenylcopper species is the rate‐limiting step of this transformation.