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Transition‐Metal‐Free Formal Decarboxylative Coupling of α‐Oxocarboxylates with α‐Bromoketones under Neutral Conditions: A Simple Access to 1,3‐Diketones
Author(s) -
He Zhen,
Qi Xiaotian,
Li Shiqing,
Zhao Yinsong,
Gao Ge,
Lan Yu,
Wu Yiwei,
Lan Jingbo,
You Jingsong
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201409361
Subject(s) - decarboxylation , reagent , chemistry , nucleophile , thermal decomposition , transition metal , coupling (piping) , computational chemistry , photochemistry , combinatorial chemistry , organic chemistry , catalysis , materials science , metallurgy
A transition‐metal‐free formal decarboxylative coupling reaction between α‐oxocarboxylates and α‐bromoketones to synthesize 1,3‐diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal‐based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the α‐bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate‐determining step is an unusual hydrogen‐bond‐assisted enolate formation by thermolysis.