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Mechanistic Study on Oxorhenium‐Catalyzed Deoxydehydration and Allylic Alcohol Isomerization
Author(s) -
Wu Di,
Zhang Yugen,
Su Haibin
Publication year - 2016
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201600118
Subject(s) - isomerization , allylic rearrangement , catalysis , alcohol , allylic alcohol , chemistry , organic chemistry
The reaction mechanism of 1,2× n ‐deoxydehydration (DODH; n =1, 2, 3 …) reactions with 1‐butanol as a reductant in the presence of methyltrioxorhenium(VII) catalyst has been investigated by DFT. The reduced rhenium compound, methyloxodihydroxyrhenium(V), serves as the catalytically relevant species in both allylic alcohol isomerization and subsequent DODH processes. Compared with three‐step pathway A, involving [1,3]‐transposition of allylic alcohols, direct two‐step pathway B is an alternative option with lower activation barriers. The rate‐limiting step of the DODH reaction is the first hydrogen transfer in methyltrioxorhenium(VII) reduction. Moreover, the increase in the distance between two hydroxyl groups in direct 1,2× n ‐DODH reactions for C4 and C6 diols results in a higher barrier height.