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The Inferior p‐Donor Ability of Phosphanyl versus Amino Substituents: Consequences on the Stability and Reactivity of Phosphanyl‐ and Aminocarbenes
Author(s) -
Goumri Stéphanie,
Leriche Yann,
Gornitzka Heinz,
Baceiredo Antoine,
Bertrand Guy
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199810)1998:10<1539::aid-ejic1539>3.0.co;2-w
Subject(s) - chemistry , iminium , deprotonation , sodium methoxide , medicinal chemistry , reactivity (psychology) , yield (engineering) , carbene , intramolecular force , enamine , salt (chemistry) , hemiaminal , stereochemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology , ion , materials science , metallurgy
Bis(diisopropylamino)(trimethylstannyl)phosphane ( 2 ) reacts with the (chloromethylene)diisopropylammonium salt 1 affording the C ‐phosphanyl‐substituted iminium salt 3 (67 % yield), which features a short C–N (1.284 Å) and a long P–C bond (1.850 Å), a planar iminium nitrogen atom and a pyramidalized phosphorus atom. Deprotonation of 3 leads to the enamine 8 (92 % yield), while addition of sodium methoxide followed by thermolysis of the resulting hemiaminal 9 (90 % yield) gives rise to the azaphosphetane 10 (85 % yield), by intramolecular CH insertion of the transiently formed (amino)(phosphanyl)carbene 6 .