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dc.contributor.authorYe, Jian-Liang
dc.contributor.authorHuang, Pei-Qiang
dc.contributor.author黄培强
dc.contributor.authorLu, Xin
dc.contributor.author吕鑫
dc.date.accessioned2011-06-20T15:16:14Z
dc.date.available2011-06-20T15:16:14Z
dc.date.issued2006-12
dc.identifier.citationJ. Org. Chem., 2007, 72 (1):35–42zh_CN
dc.identifier.issn0022-3263
dc.identifier.urihttp://dx.doi.org/doi:10.1021/jo0613683
dc.identifier.urihttps://dspace.xmu.edu.cn/handle/2288/9678
dc.description.abstract[GRAPHICS] We present a systematic theoretical investigation on the addition reaction of Grignard reagents to malimides to understand its mechanism as well as the origin of its regio- and diastereo-selectivity. The computations carried out at a hybrid density functional B3LYP/6-31G* level of theory reveal that (i) the addition of Grignard reagents with N,O-dimethylmalimide (1-methyl-3-methoxypyrrolidine-2,5-dione) occurs regioselectively at the alpha-carbonyl (C1) by passing through a cis-alpha-chelated precursor and affords stereoselectively cis-addition product, in qualitative agreement with the previous experimental observations; (ii) such regioselectivity is ascribed to the preferential chelation of Grignard reagent to the alpha-carbonyl (C1) over the coordination to the alpha'-carbonyl (C4); (iii) its unusual trans-addition, in sharp contrast to the Cram chelation-type stereoselectivity for the reaction of aliphatic alpha- or beta-alkoxy carbonyl compounds, is due primarily to the rigidity of the five-membered ring skeleton of the malimide that favors the formation of the cis-alpha-chelated precursor; and (iv) poor regioselectivity is predicted for the reaction of O-TBDMS-protected malimide (1-benzyl-3-(tert-butyldimethylsilyloxy)pyrrolidine-2,5-dione) with Grignard reagent and can be ascribed to the large steric repulsion of the bulky TBDMS group and the electronic effects of the silyl group that remarkably destabilizes the alpha-chelated precursors and the corresponding transition states.zh_CN
dc.language.isoenzh_CN
dc.publisherAMER CHEMICAL SOCzh_CN
dc.titleMechanism for the regioselective asymmetric addition of Grignard reagents to malimides: A computational explorationzh_CN
dc.typeArticlezh_CN


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