Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents

Chemical Science
Daisuke HiroseTsuyoshi Taniguchi

Abstract

Ethyl 2-arylhydrazinecarboxylates can work as organocatalysts for Mitsunobu reactions because they provide ethyl 2-arylazocarboxylates through aerobic oxidation with a catalytic amount of iron phthalocyanine. First, ethyl 2-(3,4-dichlorophenyl)hydrazinecarboxylate has been identified as a potent catalyst, and the reactivity of the catalytic Mitsunobu reaction was improved through strict optimization of the reaction conditions. Investigation of the catalytic properties of ethyl 2-arylhydrazinecarboxylates and the corresponding azo forms led us to the discovery of a new catalyst, ethyl 2-(4-cyanophenyl)hydrazinecarboxylates, which expanded the scope of substrates. The mechanistic study of the Mitsunobu reaction with these new reagents strongly suggested the formation of betaine intermediates as in typical Mitsunobu reactions. The use of atmospheric oxygen as a sacrificial oxidative agent along with the iron catalyst is convenient and safe from the viewpoint of green chemistry. In addition, thermal analysis of the developed Mitsunobu reagents supports sufficient thermal stability compared with typical azo reagents such as diethyl azodicarboxylate (DEAD). The catalytic system realizes a substantial improvement of the Mitsunobu reac...Continue Reading

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Citations

Oct 12, 2018·Organic & Biomolecular Chemistry·Rhydian H BeddoeRoss M Denton
Feb 8, 2019·Drug Testing and Analysis·Bruno Aleksander MartekJanez Košmrlj
Nov 30, 2019·Chemical Communications : Chem Comm·Zhimin XuYahui Wang
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Feb 12, 2019·The Journal of Organic Chemistry·Thomas C PickelLanny S Liebeskind
Mar 24, 2018·The Journal of Organic Chemistry·Daisuke HiroseTsuyoshi Taniguchi
May 31, 2017·The Journal of Organic Chemistry·Hai Huang, Jun Yong Kang
Aug 3, 2016·Organic Letters·Daisuke HiroseTsuyoshi Taniguchi
Jan 13, 2018·The Journal of Organic Chemistry·Min Hye Kim, Jinho Kim
Aug 29, 2019·ACS Omega·Adam PokludaRadek Cibulka
May 11, 2018·Organic Letters·Tanja StachPeter H Huy
Sep 28, 2018·Chemical Reviews·Hongchao GuoOhyun Kwon
Sep 3, 2020·Journal of the American Chemical Society·Yike ZouK N Houk
Jan 13, 2018·Organic Letters·Srirama Murthy AkondiLanny S Liebeskind

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Methods Mentioned

BETA
NMR
differential scanning calorimetry

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