1,3,2‐Diazaphospholenes Catalyze the Conjugate Reduction of Substituted Acrylic Acids

The potent nucleophilicity and remarkably low basicity of 1,3,2- diazaphospholenes (DAPs) is exploited in a catalytic, metal-free 1,4-reduction of free ,-unsaturated carboxylic acids. Notably, the reduction occurs without a prior deprotonation of the carboxylic acid moiety and hence does not consume an additional hydride equivalent. This highlights the excellent nucleophilic character and low basicity of DAP-hydrides. Func- tional groups such as Cbz group or alkyl halides which can be problematic with classical transition-metal catalysts are well tolerated in the DAP-catalyzed process. Moreover, the trans- formation is characterized by a low catalyst loading, mild reaction conditions at ambient temperature as well as fast reaction times and high yields. The proof-of-principle for a catalytic enantioselective version is described.


Published in:
ChemCatChem, 12, 17, 4262-4266
Year:
May 27 2020
Keywords:
Laboratories:


Note: The file is under embargo until: 2020-11-17


 Record created 2020-10-12, last modified 2020-10-24

Rate this document:

Rate this document:
1
2
3
 
(Not yet reviewed)