作者:Jolene P. Reid、Catherine A. McAdam、Adam J. S. Johnston、Matthew N. Grayson、Jonathan M. Goodman、Matthew J. Cook
DOI:10.1021/jo502403n
日期:2015.2.6
Two base-mediated cascade rearrangement reactions of diallyl ethers were developed leading to selective [2,3]-Wittig–oxy-Cope and isomerization–Claisen rearrangements. Both diaryl and arylsilyl-substituted 1,3-substituted propenyl substrates were examined, and each exhibits unique reactivity and different reaction pathways. Detailed mechanistic and computational analysis was conducted, which demonstrated
开发了两个碱基介导的二烯丙基醚的级联重排反应,从而导致选择性的[2,3] -Wittig-oxy-Cope和异构化-Claisen重排。对二芳基和芳基甲硅烷基取代的1,3-取代的丙烯基底物均进行了检测,每种底物均具有独特的反应性和不同的反应途径。进行了详细的机理和计算分析,表明碱和溶剂的作用是观察到的反应性和选择性的关键。交叉实验还表明,这些反应以一定程度的解离进行,并且机理途径是高度复杂的,具有多种竞争途径。