文献类型：期刊文献

英文题名：Axially Chiral N-Heterocyclic Carbene Gold(I) Complex Catalyzed Asymmetric Cycloisomerization of 1,6-Enynes

作者：Wang, Wenfeng[1,2];Yang, Jinming[1,2];Wang, Feijun[1,2];Shi, Min[1,2,3]

机构：[1]E China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]E China Univ Sci & Technol, Sch Chem & Mol Engn, Inst Fine Chem, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China

年份：2011

卷号：30

期号：14

起止页码：3859

外文期刊名：ORGANOMETALLICS

收录：;EI(收录号：20113014169957);WOS:【SCI-EXPANDED(收录号:WOS:000292847900021)，CCR-EXPANDED(收录号:WOS:000292847900021)】；

基金：We thank the Shanghai Municipal Committee of Science and Technology (08dj1400100-2), National Basic Research Program of China ((973)-2009CB825300), the Fundamental Research Funds for the Central Universities, and the National Natural Science Foundation of China for financial support (21072206, 20472096, 20872162, 20672127, 20821002, and 20732008).

语种：英文

外文关键词：X ray diffraction - Catalysis - Gold compounds - Organic compounds - Coordination reactions - Single crystals

摘要：A new class of axially chiral NHC-Au(I) complexes (1-11) has been developed from optically active BINAM and fully characterized by NMR, ESI-MS, and IR spectroscopic data, where structures of complexes 1, 2a, and 6 have been further determined by X-ray diffraction studies of their single crystals, exhibiting a nearly linear coordination geometry around the gold(I) center. Within the carried out investigations herein, the sterically less hindered gold(I) complex (aR)-6, having a pyrrolidin-1-yl group, has been realized to be the best catalyst in gold(I)-catalyzed asymmetric acetoxycyclization of 1,6-enyne 52a, giving product 53a in >99% yield with -59% ee at 0 degrees C, and the sterically less hindered gold(I) catalyst (aS)-2a is the best catalyst in the asymmetric oxidative rearrangement of 1,6-enynes, affording the corresponding aldehydes 56a,c-h in excellent yields (up to >99%) and modest enantioselectivities (31-70% cc) using PhCl as the solvent at 10 degrees C.