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Electrophilic Phosphonium Cation‐Mediated Phosphane Oxide Reduction Using Oxalyl Chloride and Hydrogen
Author(s) -
Stepen Arne J.,
Bursch Markus,
Grimme Stefan,
Stephan Douglas W.,
Paradies Jan
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201809275
Subject(s) - heterolysis , electrophile , phosphonium , chemistry , oxalyl chloride , oxide , lewis acids and bases , frustrated lewis pair , metal , medicinal chemistry , decomposition , catalysis , inorganic chemistry , combinatorial chemistry , polymer chemistry , organic chemistry
The metal‐free reduction of phosphane oxides with molecular hydrogen (H 2 ) using oxalyl chloride as activating agent was achieved. Quantum‐mechanical investigations support the heterolytic splitting of H 2 by the in situ formed electrophilic phosphonium cation (EPC) and phosphane oxide and subsequent barrierless conversion to the phosphane and HCl. The reaction can also be catalyzed by the frustrated Lewis pair (FLP) consisting of B(2,6‐F 2 C 6 H 3 ) 3 and 2,6‐lutidine or phosphane oxide as Lewis base. This novel reduction was demonstrated for triaryl and diaryl phosphane oxides providing access to phosphanes in good to excellent yields (51–93 %).