Mechanism of Pd-Catalyzed Decarbonylation of Biomass-Derived Hydrocinnamic Acid to Styrene following Activation as an Anhydride

详细信息    查看全文

• 作者：Manuel A. Ortuño ; Büşra Dereli ; Christopher J. Cramer
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 2, 2016
• 年：2016
• 卷：55
• 期：9
• 页码：4124-4131
• 全文大小：559K
• 年卷期：0
• ISSN：1520-510X

文摘

All elementary steps in the mechanism of Pd-catalyzed decarbonylation of hydrocinnamic acid through formation of a mixed anhydride species have been characterized through electronic structure calculations. Oxidative addition of the mixed anhydride to a singly or doubly ligated Pd is followed by decarbonylation, alkene formation, and catalyst regeneration. Metal-assisted deprotonation of the alkyl-Pd species by a coordinated carboxylate is predicted to be the rate-determining step; theory suggests that bulkier phosphine ligands (e.g., P(o-Tol)₃) reduce the free energy of activation substantially, while variation of the auxiliary anhydride has little influence on efficiency.