Premium
C−N Bond Insertion of a Complexed Phosphinidene into a Bis(imine) − A Novel 2,3‐Sigmatropic Shift
Author(s) -
Vlaar Mark J. M.,
Valkier Pieter,
Schakel Marius,
Ehlers Andreas W.,
Lutz Martin,
Spek Anthony L.,
Lammertsma Koop
Publication year - 2002
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 - 10.1002/1099-0690(200206)2002:11<1797::aid-ejoc1797>3.0.co;2-x
Subject(s) - phosphinidene , chemistry , imine , sigmatropic reaction , electrophile , insertion reaction , cycloaddition , bicyclic molecule , ring (chemistry) , stereochemistry , ylide , organic chemistry , catalysis
The electrophilic phosphinidene complex PhPW(CO) 5 reacts with bis(imine) 5 , possessing a single carbon spacer, to give the C−N insertion product 6 . B3LYP/6‐31G* calculations indicate that this process occurs by way of a 2,3‐sigmatropic shift from the initially formed phosphane ylide. The alternative, 1,3‐dipolar cycloaddition, followed by ring‐opening of the bicyclic structure, can be ruled out since both steps are energetically much more demanding. Ring‐closure to an azaphosphirane is also less favorable than the C−N insertion, which is in agreement with the absence of such a product in the experiment. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)