Chen Junhua, Palani Vignesh, Hoye Thomas R
Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
J Am Chem Soc. 2016 Apr 6;138(13):4318-21. doi: 10.1021/jacs.6b01025. Epub 2016 Mar 28.
We report here reactions of alkyl sulfides with benzynes thermally generated by the hexadehydro-Diels-Alder (HDDA) cycloisomerization. The initially produced 1,3-betaine (o-sulfonium/aryl carbanion) undergoes intramolecular proton transfer to generate a more stable S-aryl sulfur ylide. This can react in various manners, including engaging weak acids (HA) in the reaction medium. This can produce transient ion pairs ArSR2(+)A(-) that proceed to the products ArSR + RA. When cyclic sulfides are used, A(-) opens the ring and is incorporated into the product, an outcome that constitutes a versatile, three-component coupling process.
我们在此报告了烷基硫化物与通过六脱氢狄尔斯-阿尔德（HDDA）环异构化热生成的苯炔的反应。最初生成的1,3-内盐（邻硫鎓/芳基碳负离子）发生分子内质子转移，生成更稳定的S-芳基硫叶立德。它可以以多种方式反应，包括与反应介质中的弱酸（HA）发生反应。这会产生瞬态离子对ArSR2(+)A(-)，进而生成产物ArSR + RA。当使用环状硫化物时，A(-)会打开环并并入产物中，这一结果构成了一种通用的三组分偶联过程。
