Pot-Economy Autooxidative Condensation of 2-Aryl-2-lithio-1,3-dithianes
Vale, J. R., Rimpiläinen, T., Sievänen, E., Rissanen, K., Afonso, C. A. M., & Candeias, N. R. (2018). Pot-Economy Autooxidative Condensation of 2-Aryl-2-lithio-1,3-dithianes. Journal of Organic Chemistry, 83 (4), 1948-1958. doi:10.1021/acs.joc.7b02896
Julkaistu sarjassaJournal of Organic Chemistry
© 2018 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by American Chemical Society. Published in this repository with the kind permission of the publisher.
The autoxidative condensation of 2-aryl-2-lithio-1,3-dithianes is here reported. Treatment of 2-aryl-1,3-dithianes with n-BuLi in the absence of any electrophile leads to condensation of three molecules of 1,3-dithianes and formation of highly functionalized α-thioether ketones orthothioesters in 51–89% yields upon air exposure. The method was further expanded to benzaldehyde dithioacetals, affording corresponding orthothioesters and α-thioether ketones in 48–97% yields. The experimental results combined with density functional theory studies support a mechanism triggered by the autoxidation of 2-aryl-2-lithio-1,3-dithianes to yield a highly reactive thioester that undergoes condensation with two other molecules of 2-aryl-2-lithio-1,3-dithiane.