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A Doubly Biomimetic Synthetic Transformation: Catalytic Decarbonylation and Halogenation at Room Temperature by Vanadium Pentoxide
Author(s) -
Rana Sujoy,
Pandey Bhawana,
Dey Aniruddha,
Haque Rameezul,
Rajaraman Gopalan,
Maiti Debabrata
Publication year - 2016
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201600843
Subject(s) - halogenation , decarbonylation , chemistry , vanadium , catalysis , formic acid , pentoxide , metal , photochemistry , organic chemistry , inorganic chemistry
The halogenation of the C−H bond by metal‐oxo‐peroxo species and the decarbonylation of aldehydes by metal‐peroxo species are performed routinely in biological systems. However, metal‐mediated decarbonylative halogenation is unknown in nature. In this work, we have shown that widely available V 2 O 5 and VO(acac) 2 (acac=acetylacetonate) can catalyze decarbonylative halogenation through the generation of an intermediate vanadium‐oxo‐peroxo species, which was characterized by using 51 V NMR, UV/Vis, and resonance Raman spectroscopy. Further detection of formic acid from the reaction mixture confirmed the biomimetic aspects of decarbonylative halogenation. A detailed experimental and DFT study indicated a concerted mechanism for this decarbonylative halogenation performed under simple and mild reaction conditions.