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Chiral‐Zn(NTf 2 ) 2 ‐Complex‐Catalyzed Diastereo‐ and Enantioselective Direct Conjugate Addition of Arylacetonitriles to Alkylidene Malonates
Author(s) -
Yao Jingjing,
Liu Xiaohua,
He Peng,
Zhu Yin,
Lian Xiangjin,
Lin Lili,
Feng Xiaoming
Publication year - 2013
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.201302122
Subject(s) - deprotonation , conjugate , enantioselective synthesis , catalysis , chemistry , yield (engineering) , ligand (biochemistry) , combinatorial chemistry , medicinal chemistry , organic chemistry , ion , materials science , mathematics , mathematical analysis , biochemistry , receptor , metallurgy
Chiral N,N ′‐dioxide/Zn(NTf 2 ) 2 complexes were demonstrated to be highly effective in the direct asymmetric conjugate addition of arylacetonitriles to alkylidene malonates under mild conditions. A wide range of substrates were tolerated to afford their corresponding products in moderate‐to‐good yields with high diastereoselectivities (82:18–>99:1 d.r.) and enantioselectivities (81–99 % ee ). The reactions performed well, owing to the high Lewis acidity of the metal triflimidate and a ligand‐acceleration effect. The N,N ′‐dioxide also benefited the deprotonation process as a Brønsted base. The catalytic reaction could be performed on the gram‐scale with retention of yield, diastereoselectivity, and enantioselectivity. The products that contained functional groups were ready for further manipulation. In addition, a possible catalytic model was proposed to explain the origin of the asymmetric induction.