Transition‐Metal‐Free Formal Decarboxylative Coupling of α‐Oxocarboxylates with α‐Bromoketones under Neutral Conditions: A Simple Access to 1, 3‐Diketones1. (24th November 2014)

• Record Type: Journal Article
• Authors: He, Zhen; Qi, Xiaotian; Li, Shiqing; Zhao, Yinsong; Gao, Ge; Lan, Yu; Wu, Yiwei; Lan, Jingbo; You, Jingsong
• Is Part Of: Angewandte Chemie. Volume 127:Number 3(2015)
• Page Start: 869
• Page End: 873
• Publication Date: 2014-11-24
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201409361
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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.</p> </abstract>