Jee Dong Whan, Myung Jinnie, Little R Daniel, Han Sunkyu, Lee Hee-Yoon
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Korea.
Department of Chemistry and Biochemistry, University of California, Santa Barbara (UCSB), Santa Barbara, California 93106, United States.
Org Lett. 2022 Jun 24;24(24):4399-4403. doi: 10.1021/acs.orglett.2c01622. Epub 2022 Jun 14.
We describe a method to generate alkylidene carbenes via tetramethylammonium-fluoride-induced desilylation of silyl vinyl iodides. The reversible carbene generation from an iodovinyl anion enabled us to unearth mechanistic aspects of the trimethylenemethane (TMM) diyl cyclization reaction that could not be explored via previous methods. We observed that a slow diyl-diylophile cycloaddition can induce the reversible formation of an alkylidene carbene from the TMM diyl intermediate via a retro-cyclopropanation at ambient temperature.
我们描述了一种通过四甲基氟化铵诱导甲硅烷基乙烯基碘脱硅来生成亚烷基卡宾的方法。碘代乙烯基阴离子产生的可逆卡宾生成使我们能够揭示三甲叉甲烷（TMM）二自由基环化反应的机理，而这是以前的方法无法探究的。我们观察到，在室温下，缓慢的二自由基-亲二自由基环加成反应可以通过逆环丙烷化反应，从TMM二自由基中间体诱导亚烷基卡宾的可逆形成。
