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π‐Insertion Reactions of Benzynes into P=N and P=S Double Bonds
Author(s) -
LopezLeonardo Carmen,
Raja Rosalia,
LópezOrtiz Fernando,
Ángel del ÁguilaSánchez Miguel,
Alajarin Mateo
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201301481
Subject(s) - aryne , chemistry , phosphonium , medicinal chemistry , cycloaddition , trimethylsilyl , protonation , aryl , trifluoromethanesulfonate , demethylation , bromide , solvent , organic chemistry , alkyl , catalysis , ion , biochemistry , gene expression , dna methylation , gene
The π‐insertion reactions of in situ generated benzynes into the P=N bonds of N ‐benzyl and N ‐aryl iminophosphoranes and the P=S bonds of phosphane sulfides have been examined by using the Kobayashi benzyne precursors, (2‐trimethylsilyl)phenyl triflates. The reactions with iminophosphoranes afforded (2‐aminophenyl)phosphonium triflates under mild conditions, most probably by a [2+2]/retro [2+2] cycloaddition sequence and further N‐protonation by the solvent (CH 3 CN) or N‐phenylation by a second molecule of benzyne. The final products of the analogous reactions with P ‐OCH 3 ‐substituted iminophosphoranes were the respective (2‐aminophenyl)phosphane oxides, as result of a final O‐demethylation event of the putative phosphonium triflate. The reactions with phosphane sulfides involve a final S‐phenylation step to yield (2‐phenylthio)phenylphosphonium salts.