Département de Chimie and Centre de Recherche sur la Catalyse et les Interfaces (CERPIC), Université Laval, 1045 Avenue de la Médecine, Québec, Québec, Canada G1V 0A6.
Chem Commun (Camb). 2012 Nov 25;48(91):11250-2. doi: 10.1039/c2cc35257e.
The addition of the ambiphilic molecule Me(2)AlCH(2)PMe(2) (1) to the allenyl vinyl ketone 2 gave a trapped Nazarov reaction product. Under kinetic control, the addition of the phosphine was on the methylated carbon, contrary to expected steric and electronic considerations. Computational data pointed to hydrogen bonding between the phosphine and the methyl group guiding the regiochemistry of this reaction. This product rearranged to provide the expected, regioisomeric Nazarov product. With additional 1 this compound yielded a Michael-addition product via a retro-Nazarov process.
双膦配体 Me(2)AlCH(2)PMe(2)（1）与烯丙基乙烯基酮 2 反应得到一个被捕获的 Nazarov 反应产物。在动力学控制下，膦的加成发生在甲基化的碳原子上，这与预期的空间位阻和电子因素相违背。计算数据表明，膦和甲基之间的氢键引导了该反应的区域化学选择性。该产物重排得到了预期的、区域异构的 Nazarov 产物。用额外的 1，该化合物通过逆 Nazarov 过程生成迈克尔加成产物。
