期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 136, 期 26, 页码 9414-9423出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja503427f
关键词
-
资金
- NSF [0116050, CHE-0645381, CHE-1001589]
- Research Corporation (Scialog Award)
- National Research Foundation of Korea [R31-2012-000-10035-0]
- National Research Foundation of Korea [R31-2012-000-10035-0] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
The mechanisms of the asymmetric [4 + 1] carbocyclization of vinylallenes with carbon monoxide catalyzed by Pt(0) and Rh(I) carrying the chiral support ligand (R,R)-Me-DuPHOS (Me-DuPHOS = 1,2-bis(2,5-dimethylphosphorano)benzene) were studied using density functional theoretical models. Previously, it was observed that the (R)-stereoisomer of the 5-substituted 2-allcylidene-3-cyclopentenone products was obtained with Pt(0), but the (S)-enantiomer was formed when Rh(I) metal was used to promote the reaction. Our calculations suggest that the rate-determining step in both cases consists of a C-C coupling between the vinyl end of the vinylallene substrate and carbon monoxide that is accompanied by charge transfer from the metal center to the organic substrate. The reason that the two metals give different enantiomer products lies in the very different geometries of the metal centers in the transition state. The platinum center adopts a square-planar geometry throughout the C-C coupling reaction, which forces the carbonyl to migrate from the metastable, pseudoaxial position into the equatorial plane. During this migration, the carbonyl encounters the spatial constraints caused by the asymmetric DuPHOS ligand, while the vinylallene fragment is pushed away from the metal center. Thus, regardless of the steric demands of the organic substrate, the transition state that places the vinyl in a position that allows the CO to move into the sterically less crowded side of the molecule is preferred. Rh, on the other hand, maintains a square-pyramidal geometry throughout the reaction, keeping the CO ligand at the axial coordination site. The C-C coupling is accomplished by pulling the vinylallene substate closer to the metal and, as a result, the transition state that causes the least amount of steric dashes between the substrate and the DuPHOS ligand is favored, which affords the (S)-enantiomeric product.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据