1,4-Bis-Dipp/Mes-1,2,4-Triazolylidenes: Carbene Catalysts That Efficiently Overcome Steric Hindrance in the Redox Esterification of α- and β-Substituted α,β-Enals

Journal of the American Chemical Society
Veera Reddy YathamAlbrecht Berkessel

Abstract

As reported by Scheidt and Bode in 2005, sterically nonencumbered α,β-enals are readily converted to saturated esters in the presence of alcohols and N-heterocyclic carbene catalysts, e.g., benzimidazolylidenes or triazolylidenes. However, substituents at the α- or β-position of the α,β-enal substrate are typically not tolerated, thus severely limiting the substrate spectrum. On the basis of our earlier mechanistic studies, a set of N-Mes- or N-Dipp-substituted 1,2,4-triazolium salts were synthesized and evaluated as (pre)catalysts in the redox esterification of various α- or β-substituted enals. In particular the 1,4-bis-Mes/Dipp-1,2,4-triazolylidenes overcome the above limitations and efficiently catalyze the redox esterification of a whole series of α/β-substituted enals hitherto not amenable to NHC-catalyzed transformations. The synthetic value of 1,4-bis-Mes/Dipp-1,2,4-triazolylidenes is further demonstrated by the one-step bicyclization of 10-oxocitral to (racemic) nepetalactone in diastereomerically pure form.

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Citations

Feb 16, 2016·Journal of the American Chemical Society·Mathias PaulAlbrecht Berkessel
May 25, 2016·Journal of the American Chemical Society·Xingkuan ChenYonggui Robin Chi
Apr 3, 2016·Chemistry : a European Journal·David L CramerArmido Studer
May 3, 2018·Chemistry : a European Journal·Małgorzata KrasowskaAlexander A Auer
Oct 2, 2020·Angewandte Chemie·Marcel A Strauss, Hermann A Wegner
Oct 21, 2020·Chemistry : a European Journal·Markus BurschDaniel B Werz
Jun 15, 2021·Chemical Science·Xiaolin PengZhichao Jin
Jan 7, 2020·Organic Letters·Wacharee HarnyingAlbrecht Berkessel
Aug 25, 2017·The Journal of Organic Chemistry·Zhen LiJin-Pei Cheng
May 6, 2017·Journal of the American Chemical Society·Jiean ChenYong Huang
Oct 1, 2021·Journal of the American Chemical Society·Mitchell T Lee, Gojko Lalic

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