控制二氢萘 C-H 功能化与环丙烷化的因素。
Controlling factors for C-H functionalization versus cyclopropanation of dihydronaphthalenes.
机构信息
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
出版信息
J Org Chem. 2010 Mar 19;75(6):1927-39. doi: 10.1021/jo902644f.
Abstract
Rhodium(II)-catalyzed reactions of vinyldiazoacetates with dihydronaphthalenes were systematically studied. These substrates underwent cyclopropanantion and/or the combined C-H activation/Cope rearrangement in good overall yield and with good diastereo- and enantiocontrol. The selectivity of these reactions was profoundly influenced by the nature of the chiral catalyst, the vinyldiazoacetate, and the dihydronaphthalene. The best combinations for achieving the highest selectivity in the cyclopropanation and the combined C-H activation/Cope rearrangement of 1,2-dihydronaphthalenes are methyl 2-diazopent-3-enoate (2a)/Rh(2)(S-DOSP)(4) and methyl 3-(tert-butyldimethylsilyloxy)-2-diazopent-3-enoate (2b)/Rh(2)(S-PTAD)(4). These combinations are very effective at enantiodivergent reactions of 1-methyl-1,2-dihydronaphthalenes.
摘要
系统研究了铑（II）催化的乙烯基重氮乙酸酯与萘烷的反应。这些底物经历了环丙烷化和/或 C-H 活化/Cope 重排，总收率良好，具有良好的非对映选择性和对映选择性。这些反应的选择性受到手性催化剂、乙烯基重氮乙酸酯和萘烷的性质的深刻影响。对于实现 1,2-二氢萘的环丙烷化和 C-H 活化/Cope 重排的最高选择性的最佳组合是甲基 2-二氮戊-3-烯酸酯（2a）/Rh（2）（S-DOSP）（4）和甲基 3-（叔丁基二甲基甲硅烷基氧基）-2-二氮戊-3-烯酸酯（2b）/Rh（2）（S-PTAD）（4）。这些组合在 1-甲基-1,2-二氢萘的对映体发散反应中非常有效。
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