Mechanism of N-heterocylic carbene-catalyzed annulation of allenals with chalcones to 3-pyrancarbaldehydes or cyclopentene

被引:24
|
作者
Wei, Xiaoxiao [1 ]
Fang, Ran
Yang, Lizi
机构
[1] Lanzhou Univ, Coll Chem & Chem Engn, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China
基金
中国国家自然科学基金;
关键词
TO-TAIL DIMERIZATION; MAIN-GROUP THERMOCHEMISTRY; BOND-CLEAVAGE; DENSITY FUNCTIONALS; RING EXPANSION; STEREOSELECTIVE-SYNTHESIS; CONJUGATE-ADDITION; METHYL ACRYLATE; ONE-POT; ACTIVATION;
D O I
10.1039/c5cy00407a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The reaction mechanisms of N-heterocylic carbene (NHC)-catalyzed annulation to 3-pyrancarbaldehydes or cyclopentene were theoretically analyzed. Different from what has been reported for normal aldehydes or enals, our calculation results revealed that the intermediate results from the conjugate addition to the central carbon atom of the allene moiety, instead of forming the Breslow intermediate. The next step, 1,4-addition of the chalcone, resulted in the formation of an enolate anion intermediate. Then, intramolecular conjugate addition and elimination of the NHC catalyst afforded the final product. In addition, the computed results showed good agreement with the experimental evidence, suggesting that both the existence of an allene structure and charge distribution play a crucial role in the outcome of chemoselectivity and involvement of operative intermediates in the reaction pathway.
引用
收藏
页码:3352 / 3362
页数:11
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