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Methylene‐Azaphosphirane as a Reactive Intermediate
Author(s) -
Slootweg J. Chris,
Vlaar Mark J. M.,
Vugts Danielle J.,
Eichelsheim Tanja,
Merhai Winita,
de Kanter Frans J. J.,
Schakel Marius,
Ehlers Andreas W.,
Lutz Martin,
Spek Anthony L.,
Lammertsma Koop
Publication year - 2005
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.200500207
Subject(s) - phosphinidene , methylene , chemistry , sigmatropic reaction , reactive intermediate , stereochemistry , medicinal chemistry , crystal structure , crystallography , catalysis , organic chemistry
Reaction of the transient phosphinidene complexes R‐PW(CO) 5 with N‐substituted‐diphenylketenimines leads unexpectedly to the novel 2‐aminophosphindoles, as confirmed by an X‐ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene‐azaphosphirane intermediate was found by using the iron‐complexed phosphinidene i Pr 2 N‐PFe(CO) 4 , which affords the 2‐aminophosphindole together with the novel methylene‐2,3‐dihydro‐1 H ‐benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene‐azaphosphirane yields both phosphorus heterocycles by way of a [1,5]‐ or [1,3]‐sigmatropic shift, respectively, followed by a H‐shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents.