Electrochemical Reductive Smiles Rearrangement for C-N Bond Formation
A conceptually new and synthetically valuable radical Smiles rearrangement reaction is reported under undivided electrolytic conditions. This protocol employs an entirely new strategy for the electrochemical radical Smiles rearrangement. Remarkably, an amidyl radical generated from the cleavage of the N-O bond under reductive electrolytic conditions plays a crucial role in this transformation. Various hydroxylamine derivatives bearing different substituents are suitable in this electrochemical transformation, furnishing the corresponding amides in up to 86% yield.
Chang, Xihao,Zhang, Qinglin,Guo, Chang
p. 10 - 13
(2019/01/04)
Formal Aniline Synthesis from Phenols through Deoxygenative N-Centered Radical Substitution
Phenolic, lignin-derived substrates have emerged as desirable biorenewable chemical feedstocks for coupling reactions. A radical-mediated conversion of phenol derivatives to anilines is reported, using unfunctionalized hydroxamic acids as the N-centered radical source. The applicability of this triethyl phosphite mediated O-atom transfer approach, which tolerates a range of steric and electronic demands to naturally occurring phenols and lignin models, has been demonstrated in this work to access the corresponding aniline derivatives.
Lardy, Samuel W.,Luong, Kristine C.,Schmidt, Valerie A.
p. 15267 - 15271
(2019/12/11)
Efficient Aryl Migration from an Aryl Ether to a Carboxylic Acid Group To Form an Ester by Visible-Light Photoredox Catalysis
We have developed a highly efficient aryl migration from an aryl ether to a carboxylic acid group through retro-Smiles rearrangement by visible-light photoredox catalysis at ambient temperature. Transition metals and a stoichiometric oxidant and base are avoided in the transformation. Inspired by the high efficiency of this transformation and the fundamental importance of C?O bond cleavage, we developed a novel approach to the C?O cleavage of a biaryl ether to form two phenolic compounds, as demonstrated by a one-pot, two-step gram-scale reaction under mild conditions. The aryl migration exhibits broad scope and can be applied to the synthesis of pharmaceutical compounds, such as guacetisal. Primary mechanistic studies indicate that the catalytic cycle occurs by a reductive quenching pathway.
Wang, Shao-Feng,Cao, Xiao-Ping,Li, Yang
p. 13809 - 13813
(2017/10/24)
Palladium-catalyzed intramolecular decarboxylative coupling of arene carboxylic acids/esters with aryl bromides
Give me a ring? An efficient approach has been developed for the intramolecular decarboxylative coupling of arene carboxylic acids/esters with aryl bromides catalyzed by palladium (see scheme). From a synthetic viewpoint, this method is highly attractive because the catalyst loading is low, the optimized reaction conditions are mild, and the substrate scope is broad. Copyright
The invention is directed to compounds of Formula (I) useful as delta and mu opioid receptor modulators. Pharmaceutical and veterinary compositions and methods of treating mild to severe pain and various diseases using compounds of the invention are also
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Page/Page column 25; 26
(2008/06/13)
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