Allylation of Phosphorus, Arsenic, and Antimony Trihalides by Allylic Stannanes. Synthesis, Spectroscopic Characterization, and Quantum Chemical Investigations of Allylic Phosphines, Arsines, and Stibines
作者:Stéphanie Le Serre、Jean-Claude Guillemin、Tamás Karpati、László Soos、László Nyulászi、Tamás Veszprémi
DOI:10.1021/jo971000t
日期:1998.1.1
efficient allylation reagents of electrophiles, allylic dichlorostibines 4a,c reacted with benzaldehyde to lead to the corresponding homoallyl alcohols. Syn and anti products were mainly produced starting from crotyldichlorostibines (4e,e'). The primary allylic phosphines 7a-f, arsines 8a-f, and stibines 9a,bhave been prepared by the chemoselective reduction of the corresponding allylic dihalophosphines
烯丙基三丁基锡烷与磷,砷或锑三卤化物之间的反应导致相应的烯丙基膦,rs或锑二卤化物。对于磷衍生物,仅观察到γ-区域选择,如(1-甲基-2-丙烯基)-(2e,f)或(1,1-二甲基-2-丙烯基)二卤代膦酸酯(2g,h)的形成所示)分别从巴豆基锡烷1c,c'或异戊烯基锡烷1d和PCl(3)或PBr(3)开始。在80摄氏度加热时,其中的某些膦可生成相应的热力学产物。还制备了烯丙基二氯ar氨酸3a-d,并且在室温下将动力学化合物3c,d完全重排为相应的巴豆基-(3e,e')和异戊二烯基二氯ar啶(3f)。对于锑衍生物,即使在低温(-90摄氏度)下,观察到仅包含热力学产物的粗混合物。虽然烯丙基二卤代膦和-ar氨酸不是亲电试剂的有效烯丙基化试剂,但烯丙基二氯雌激素4a,c与苯甲醛反应生成相应的均烯丙基醇。顺式和反式产品主要是从巴豆基二氯stibines(4e,e')开始生产的。通过用四甘醇二甲醚中的L