dc.contributor.author | Ye, Jian-Liang | |
dc.contributor.author | Huang, Pei-Qiang | |
dc.contributor.author | 黄培强 | |
dc.contributor.author | Lu, Xin | |
dc.contributor.author | 吕鑫 | |
dc.date.accessioned | 2011-06-20T15:16:14Z | |
dc.date.available | 2011-06-20T15:16:14Z | |
dc.date.issued | 2006-12 | |
dc.identifier.citation | J. Org. Chem., 2007, 72 (1):35–42 | zh_CN |
dc.identifier.issn | 0022-3263 | |
dc.identifier.uri | http://dx.doi.org/doi:10.1021/jo0613683 | |
dc.identifier.uri | https://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.iso | en | zh_CN |
dc.publisher | AMER CHEMICAL SOC | zh_CN |
dc.title | Mechanism for the regioselective asymmetric addition of Grignard reagents to malimides: A computational exploration | zh_CN |
dc.type | Article | zh_CN |