One-Pot Synthesis of Silylated Enol Triflates from Silyl Enol Ethers for Cyclohexynes and 1,2-Cyclohexadienes
One-Pot Synthesis of Silylated Enol Triflates from Silyl Enol Ethers for Cyclohexynes and 1,2-Cyclohexadienes
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DOI：
10.1002/ejoc.201800353
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发表时间：
2018-07-06
影响因子：
2.8
通讯作者：
Mori, Atsunori
中科院分区：
文献类型：
--
作者：
Inoue, Kazuki;Nakura, Ryo;Mori, Atsunori
描述了基于硅烯醇醚的一锅重排，然后形成三酸烯醇的区域控制合成应变环己炔和1,2-环己二烯前体。用LDA和tBuOK联合处理硅烯醇醚，导致硅基迁移生成-硅烯醇酯，用Comins试剂处理得到相应的烯醇三酸酯。在室温下，瞬时硅烷基化的烯酸锂在化学量的水的存在下，在一小时内顺利异构化，在一个锅中为环己烯提供了前体。硅烷基、烯酸锂的异构化以及这些前体对这些张力分子的区域控制生成的影响也进行了研究。
Regiocontrolled synthesis of precursors for strained cyclohexynes and 1,2-cyclohexadienes is described based on one-pot rearrangement of silyl enol ether followed by formation of enol triflate. Treatment of silyl enol ether with a combination of LDA and tBuOK led to the migration of the silyl group to generate -silyl enolate, which was treated with Comins' reagent to provide the corresponding enol triflate. The transient -silylated lithium enolate was smoothly isomerized in the presence of stoichiometric amount of water within one hour at room temperature, providing precursors for cyclohexynes exclusively in one pot. Effects of silyl groups, isomerization of the lithium enolate, and regiocontrolled generation of these precursors for these strained molecules were also investigated.