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A Convenient Synthesis of 1,2,4‐ and 1,3,4‐Azadiphospholes
Author(s) -
Suter Riccardo,
Benkő Zoltán,
Grützmacher Hansjörg
Publication year - 2016
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.201602864
Subject(s) - steric effects , yield (engineering) , chemistry , chloride , carbon monoxide , ring (chemistry) , medicinal chemistry , inorganic chemistry , combinatorial chemistry , organic chemistry , catalysis , materials science , metallurgy
A new synthetic route to functionalized neutral and anionic azadiphospholes from easily accessible starting materials is described. Equimolar reaction of Na(OCP) and N ‐(2,6‐dimethylphenyl)pivalimidoyl chloride 2 a cleanly affords the imidoxy‐functionalized 1,2,4‐azadiphosphole 3 a . Using Na(OCP) and imidoyl chloride in a 2:1 ratio leads to an anionic four‐membered ring Na[ 4 a ], which has been structurally characterized. During 16 h at room temperature, Na[ 4 a ] rearranges to the anionic 1,3,4‐azadiphospholide Na[ 5 a ] with release of carbon monoxide. Applying the more sterically demanding N ‐(2,6‐diisopropylphenyl)pivalimidoyl chloride allows isolation of the 1,3,4‐azadiphospholide Na[ 5 b ] in good yield (>70 %). Possible mechanisms leading to the new isomeric azadiphospholides have been investigated with the aid of high‐level composite calculations.