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Highly Enantioselective Catalytic Asymmetric [2+2] Cycloadditions of Cyclic α‐Alkylidene β‐Oxo Imides with Ynamides
Author(s) -
Enomoto Kazuaki,
Oyama Harufumi,
Nakada Masahisa
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.201406189
Subject(s) - imide , enantioselective synthesis , intramolecular force , cycloaddition , chemistry , nitrile , catalysis , reactivity (psychology) , substrate (aquarium) , hydrogen bond , amide , medicinal chemistry , stereochemistry , organic chemistry , molecule , medicine , oceanography , alternative medicine , pathology , geology
Highly enantioselective catalytic asymmetric [2+2] cycloadditions of cyclic α‐alkylidene β‐oxo imides with ynamides are described. The high reactivity of the cyclic α‐alkylidene β‐oxo imide allows the [2+2] cycloadditions of a hindered substrate with unreactive ynamides at low temperature. The X‐ray crystallographic analysis of the product suggests that the enantioselectivity of the [2+2] cycloaddition can be well explained by the chelate model comprising the intramolecular hydrogen bond, wherein the cyclic α‐alkylidene β‐oxo imide coordinates with Cu II through the two imide carbonyls. The imide group in the product can be transformed to amide, nitrile, and ester groups; moreover, it is removable.