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Glycerol Boosted Rh‐Catalyzed Hydroaminomethylation Reaction: A Mechanistic Insight
Author(s) -
SerranoMaldonado Alejandro,
DangBao Trung,
Favier Isabelle,
GuerreroRíos Itzel,
Pla Daniel,
Gómez Montserrat
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001978
Subject(s) - chemistry , catalysis , enamine , hydroformylation , phosphine , aldol condensation , glycerol , reductive amination , olefin fiber , rhodium , selectivity , organic chemistry , combinatorial chemistry
We report a Rh‐catalyzed hydroaminomethylation reaction of terminal alkenes in glycerol that proceeds efficiently under mild conditions to produce the corresponding amines in relatively high selectivity towards linear amines, moderate to excellent yields by using a low catalyst loading (1 mol % [Rh], 2 mol % phosphine) and relative low pressure (H 2 /CO, 1:1, total pressure 10 bar). This work sheds light on the importance of glycerol in enabling enamine reduction via hydrogen transfer. Moreover, evidence for the crucial role of Rh as chemoselective catalyst in the condensation step has been obtained for the first time in the frame of the hydroaminomethylation reaction by precluding deleterious aldol condensation reactions. The hydroaminomethylation proceeds under a molecular regime; the outcome of catalytically active species into metal‐based nanoparticles renders the catalytic system inactive.