在制备 une serie d'acides carboxyliques allyliques a partir des ocoxyliques par un processus en deux etapes 等价物 a: 1) une 反应 ene avec l'oxomalonate de diethyle conduisant a l'ester α-hydroxymalonique; 2) une bisdecarboxylation oxydante de ce dernier
In this study, the heterogeneously catalyzed alkoxycarbonylation of olefins with CO2 based on a supported ionic-liquid-phase (SILP) strategy is reported for the first time. An [Ru]@SILP catalyst was accessed by immobilization of ruthenium complex on a SILP, wherein imidazolium chloride was chemically integrated at the surface or in the channels of the silica gel support. An active Ru site was generated
Remarkably Facile Solvolyses of Triflates via Carbocationic Processes in Dimethyl Sulfoxide
作者:Xavier Creary、Elizabeth A. Burtch
DOI:10.1021/jo0356558
日期:2004.2.1
A number of triflates have been shown to undergo clean pseudo-first-order solvolysis reactions in DMSO-d6 to give products derived from carbocationic intermediates. Thus, t-BuCH(OTf)CO-t-Bu (5) and t-BuCH2OTf (9) react readily in DMSO-d6 at 25 °C to give a rearranged oxosulfonium salts, and subsequent alkene products where methyl migration to the incipient cationic center occurs. t-BuCH(OTf)CO2CH3
已显示许多三氟甲磺酸酯在DMSO- d 6中进行了干净的拟一级溶剂分解反应,得到了衍生自碳阳离子中间体的产物。因此,t -BuCH(OTf)CO- t- Bu(5)和t -BuCH 2 OTf(9)在DMSO- d 6中在25°C下容易反应,得到重排的氧ulf盐,以及随后出现甲基迁移的烯烃产物到起始阳离子中心发生。t -BuCH(OTf)CO 2 CH 3(14)得到类似的重排产物,以及1-甲基环丙基三氟甲磺酸酯(21)得到开环的烯丙基氧ulf盐。这些主要三氟甲磺酸酯反应,经由ķ Δ通路。6-甲基双环[3.1.0]己-6-三氟甲磺酸酯(23),双环[2.2.1庚-1-基三氟甲磺酸酯(24),1,6-甲基[10]三氟甲磺酸十一烷基酯(25), (CH 3)2 C(OTf)CO 2 CH 3(26)和(CH 3)2 CCN(OTf)(29)都在DMSO- d 6中反应生成碳正离子衍生的产物。PhCH(OTf)CF