Institute of Organic Chemistry and Center for Molecular Biosciences, Leopold-Franzens-University Innsbruck , Innrain 80-82 , 6020 Innsbruck , Austria.
Department of Chemistry and Pharmacy , Ludwig-Maximilians-University Munich , Butenandtstrasse 5-13 , 81377 Munich , Germany.
J Am Chem Soc. 2019 Aug 28;141(34):13352-13357. doi: 10.1021/jacs.9b07729. Epub 2019 Aug 16.
Here we present a comprehensive study on the [3+2]-cycloaddition of thiocarbonyl ylides with a wide variety of alkenes and alkynes. The obtained dihydro- and tetrahydrothiophene products serve as exceptionally versatile intermediates providing access to thiophenes, dienes, dendralenes, and -quarternary carbon centers. The use of high-pressure conditions enables thermally unstable, sterically encumbered or moderately reactive substrates to undergo the cycloaddition under mild conditions, thereby increasing the yield by up to 58%. In addition, we showcase its utility by the formal syntheses of the pharmaceuticals NGB 4420 and tenilapine.
在这里，我们展示了对硫羰基叶立德与各种烯烃和炔烃的[3+2]-环加成的综合研究。得到的二氢和四氢噻吩产物是非常通用的中间体，可用于合成噻吩、二烯、树状烯和 -季碳原子中心。使用高压条件可以使热不稳定、空间位阻大或中等反应性的底物在温和条件下进行环加成，从而将产率提高高达 58%。此外，我们通过 NGB 4420 和替尼拉平等药物的形式合成展示了其应用。
