期刊
TETRAHEDRON
卷 84, 期 -, 页码 -出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.tet.2021.132005
关键词
All-carbon quaternary stereogenic centers; Organocatalysis; Asymmetric conjugate addition; Nitroalkanes; Primary amine-thiourea; Cyclic enones
资金
- National Key R&D Program of China [2017YFA0207302]
- National Natural Science Foundation of China [22071204, 21931010]
- Program for Changjiang Scholars and Innovative Research Team in University of the Ministry of Education, China
A versatile organocatalytic asymmetric conjugate addition of nitroalkanes to beta-substituted cyclic alpha,beta-enones has been developed, yielding cyclic ketones with all-carbon quaternary stereogenic centers. The method shows wide substrate scope and good functional group tolerance, allowing quick access to multi-functionalized chiral compounds. The synthetic potential of the method was demonstrated by one-step transformations of the nitro-ketone adducts to other classes of compounds.
A versatile organocatalytic asymmetric conjugate addition of nitroalkanes to beta-substituted cyclic alpha,beta-enones to yield cyclic ketones bearing all-carbon quaternary stereogenic centers at beta-C has been developed. This is an extension of the method that we developed during the total synthesis of (-)-haliclonin A, which features the employment of structurally relatively simple, cheap and easily available primary amine-thiourea derived from (R,R)-1,2-diaminocyclohexane as the chiral catalyst. The method shows wide substrate scope, good functional group tolerance, which allows a quick access to multi-functionalized chiral compounds. The synthetic potential of the method was demonstrated by one-step transformations of the nitro-ketone adducts to four other classes of compounds. The absolute configurations of adducts were determined by comparison of both the retention time of chiral HPLC analysis and sense of specific optical rotation with those of a known compound. The enantioselective control mechanism was rationalized based on the DFT computational studies. (c) 2021 Elsevier Ltd. All rights reserved.
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