文献类型：期刊文献

英文题名：Perchloric Acid Catalyzed Homogeneous and Heterogeneous Addition of β-Dicarbonyl Compounds to Alcohols and Alkenes and Investigation of the Mechanism

作者：Liu, Pei Nian[1,2,3];Dang, Li[4];Wang, Qing Wei[1,2];Zhao, Shu Lei[1,2];Xia, Fei[1,2];Ren, Yu Jie[1,2];Gong, Xue Qing[1,2];Chen, Jun Qin[1,2]

机构：[1]E China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]E China Univ Sci & Technol, Inst Fine Chem, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[3]Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China;[4]Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China

年份：2010

卷号：75

期号：15

起止页码：5017

外文期刊名：JOURNAL OF ORGANIC CHEMISTRY

收录：;EI(收录号：20103113119185);WOS:【SCI-EXPANDED(收录号:WOS:000280398100015)，CCR-EXPANDED(收录号:WOS:000280398100015)】；

基金：We thank Prof. Chak-Po Lau in the Hong Kong Polytechnic University and Prof. Zhenyang Lin in the Hong Kong University of Science & Technology for the generous helps and discussions. We greatly appreciate one of the reviewers for her/his thorough revisions for this paper. This work was supported financially by NSFC (Project No. 20902020), the Shanghai Pujiang Talent Program (Project No. 09PJ1403500) and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Silica gel - Catalysis - Catalysts - Hydrocarbons - Ketones

摘要：The direct addition of various beta-dicarbonyl compounds to a series of secondary alcohols and alkenes has been achieved using 1 mol % perchloric acid (HClO4) as the catalyst. The HClO4-catalyzed reactions could be conveniently conducted in commercial solvent and gave moderate to excellent yields. Moreover, the silica gel-supported HClO4 could also catalyze the heterogeneous addition for a series of substrates with similar or even higher yields in comparison with the homogeneous ones. The supported catalyst could be readily recovered and reused for four runs. Furthermore, the mechanism of the HClO4-catalyzed addition of the beta-diketone to alcohol was investigated, and an S(N)1 mechanism was proved unambiguously for the first time through a series of experiments. The discrimination of catalytic abilities among different Bronsted acids was also rationalized by DFT calculations.