Hydropersulfides: H-Atom Transfer Agents Par Excellence
作者:Jean-Philippe R. Chauvin、Markus Griesser、Derek A. Pratt
DOI:10.1021/jacs.7b02571
日期:2017.5.10
biotransmitter hydrogen sulfide (H2S) and disulfides (RSSR) and/or sulfenicacids (RSOH). RSSH have been investigated for their ability to store H2S in vivo and as a line of defense against oxidative stress, from which it is clear that RSSH are much more reactive to two-electron oxidants than thiols. Herein we describe the results of our investigations into the H-atom transfer chemistry of RSSH, contrasting
Direct Deamination of Primary Amines via Isodiazene Intermediates
作者:Kathleen J. Berger、Julia L. Driscoll、Mingbin Yuan、Balu D. Dherange、Osvaldo Gutierrez、Mark D. Levin
DOI:10.1021/jacs.1c09779
日期:2021.10.27
here a reaction that selectively deaminates primary amines and anilines under mild conditions and with remarkable functional group tolerance including a range of pharmaceutical compounds, amino acids, amino sugars, and natural products. An anomeric amide reagent is uniquely capable of facilitating the reaction through the intermediacy of an unprecedented monosubstituted isodiazene intermediate. In addition
combination of “TiCl2(cat)” and Zn (cat=catecholate) facilitates the homolytic cleavage of “non-activated” alcohol C−O bonds. All aliphatic primary, secondary and tertiary alcohols serve as good substrates. This method was applied to radical conjugate addition reactions successfully, and mechanistic studies indicate that alkyl chlorides are not intermediates. The active species is a 1 : 2 complex of alkoxide