School of Pharmacy, University of Wisconsin, Madison, 53705, USA.
Chem Soc Rev. 2012 Dec 7;41(23):7698-711. doi: 10.1039/c2cs35235d.
Transition metal-catalyzed acyloxy migration of propargylic esters offers versatile entries to allene and vinyl carbene intermediates for various fascinating subsequent transformations. Most π-acidic metals (e.g. gold and platinum) are capable of facilitating these acyloxy migration events. However, very few of these processes involve redox chemistry, which are well-known for most other transition metals such as rhodium. The coupling of acyloxy migration of propargylic esters with oxidative addition, migratory insertion, and reductive elimination may lead to ample new opportunities for the design of new reactions. This tutorial review summarizes recent developments in Rh-catalyzed 1,3- and 1,2-acyloxy migration of propargylic esters in a number of cycloaddition reactions. Related Au- and Pt-catalyzed cycloadditions involving acyloxy migration are also discussed.
过渡金属催化炔丙酯的酰氧基迁移为烯丙基和乙烯基卡宾中间体提供了各种有趣的后续转化的多功能入口。大多数π-酸性金属（例如金和铂）能够促进这些酰氧基迁移反应。然而，这些过程中很少涉及氧化还原化学，这在大多数其他过渡金属（如铑）中是众所周知的。炔丙酯的酰氧基迁移与氧化加成、迁移插入和还原消除的偶联可能为设计新反应提供大量新机会。本综述总结了 Rh 催化的炔丙酯的 1,3-和 1,2-酰氧基迁移在一系列环加成反应中的最新进展。还讨论了涉及酰氧基迁移的相关 Au 和 Pt 催化的环加成。
