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	Mechanism for the regioselective asymmetric addition of Grignard reagents to malimides: A computational exploration
	Ye, Jian-Liang ; Huang, Pei-Qiang ; Huang PQ(黄培强) ; Lu, Xin ; Lv X(吕鑫)
	2006-12
英文摘要	[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.
语种	英语
出版者	AMER CHEMICAL SOC
内容类型	期刊论文
源URL	[http://dx.doi.org/doi:10.1021/jo0613683]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Ye, Jian-Liang,Huang, Pei-Qiang,Huang PQ,et al. Mechanism for the regioselective asymmetric addition of Grignard reagents to malimides: A computational exploration[J],2006.
APA	Ye, Jian-Liang,Huang, Pei-Qiang,黄培强,Lu, Xin,&吕鑫.(2006).Mechanism for the regioselective asymmetric addition of Grignard reagents to malimides: A computational exploration..
MLA	Ye, Jian-Liang,et al."Mechanism for the regioselective asymmetric addition of Grignard reagents to malimides: A computational exploration".(2006).

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