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Guanidine–Copper Complex Catalyzed Allylic Borylation for the Enantioconvergent Synthesis of Tertiary Cyclic Allylboronates
Author(s) -
Ge Yicen,
Cui XiYang,
Tan Siu Min,
Jiang Huan,
Ren Jingyun,
Lee Nicholas,
Lee Richmond,
Tan ChoonHong
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201813490
Subject(s) - borylation , chemistry , guanidine , allylic rearrangement , copper , catalysis , denticity , enantioselective synthesis , organic chemistry , metal , aryl , alkyl
An enantioconvergent synthesis of chiral cyclic allylboronates from racemic allylic bromides was achieved by using a guanidine–copper catalyst. The allylboronates were obtained with high γ/α regioselectivities (up to 99:1) and enantioselectivities (up to 99 % ee ), and could be further transformed into diverse functionalized allylic compounds without erosion of optical purity. Experimental and DFT mechanistic studies support an S N 2′ borylation process catalyzed by a monodentate guanidine–copper(I) complex that proceeds through a special direct enantioconvergent transformation mechanism.