摘要：The GSK Carbon Neutral Laboratories forSustainable Chemistry, University of Nottingham, Nottingham NG7 2TU, UnitedKingdom;

转自：康龙化成

Iterative One-Carbon Homologationof Unmodified Carboxylic Acids

Emilie Wheatley,† Heorhii Melnychenko,†and Mattia Silvi*

The GSK Carbon Neutral Laboratories forSustainable Chemistry, University of Nottingham, Nottingham NG7 2TU, UnitedKingdom;

School of Chemistry, University ofNottingham, Nottingham NG7 2RD, United Kingdom;

† E.W. and H.M. contributed equally.

—J. Am. Chem. Soc. 2024, 10.1021/jacs.4c13630

Recommended by Chunlei Lu_ MC2

KEYWORDS: Photocatalysis (反应类型),one-carbon homologation (反应类型),C(sp3)− C(sp3) (成键类型),Carboxylic acids (原料),nitroethylene (原料),Carboxylic acids (产物),Cu(MeCN)4BF4 (催化剂)，C-NO2 cleavage (其他)

ABSTRACT: Theone-carbon homologation of carboxylic acids is a valuable route to constructfamilies of homologues, which play fundamental roles in chemistry and biology.However, known procedures are based on multistep sequences, use harshconditions or are limited in scope. Thus, almost a century after the discoveryof the original Arndt−Eistert homologation sequence, a general method todirectly convert carboxylic acids into their corresponding homologues remainselusive. Exploiting the photoredoxreactivity of nitroethylene, we disclose a practical visible-light-inducedhomologation of unmodified carboxylic acids. Iterations of the procedure revealan exceptionally tunable strategy for the construction of inert carbon spacers,opening new opportunities in synthesis.

Carboxylic Acid Homologation, Relevance,Challenges, and This Strategy

Inconclusion, Prof. Mattia Silvi etal have introduced a direct and general procedure for homologationof unmodified carboxylic acids.The methodology features a wide scope andenables late-stagehomologation of complex molecules, opening the route to iterative homologation chemistry. Thesynthetic versatility of this methodology was demonstrated through thesynthesis of a variety of unnatural amino acids and the tunableintroduction of inert carbon spacers into bioactive molecules for biologicalchemistry applications.The homologation approach presented in this report is expected to provide avaluable tool in synthesis.

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