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Catalytic Asymmetric Three‐component Hydroacyloxylation/ 1,4‐Conjugate Addition of Ynamides
Author(s) -
Li Xiangqiang,
Jiang Mingyi,
Zhan Tangyu,
Cao Weidi,
Feng Xiaoming
Publication year - 2020
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.202000503
Subject(s) - conjugate , component (thermodynamics) , catalysis , computer science , chemistry , mathematics , physics , organic chemistry , mathematical analysis , thermodynamics
A highly enantioselective three‐component hydroacyloxylation/1,4‐conjugate addition of ortho ‐hydroxybenzyl alcohols, ynamides and carboxylic acids was developed under mild reaction conditions in the presence of a chiral N,N′ ‐dioxide/Sc(OTf) 3 complex, which went through in situ generated ortho ‐quinone methides with α‐acyloxyenamides, delivering a range of corresponding chiral α‐acyloxyenamides derivatives containing gem (1,1)‐diaryl skeletons in moderate to good yields with excellent ee values. The scale‐up experiment and further derivation showed the practicality of this catalytic system. In addition, a possible catalytic cycle and transition state model was proposed to elucidate the origin of the stereoselectivity based on X‐ray crystal structure of the α‐acyloxyenamide intermediate and product.