The Inferior p-Donor Ability of Phosphanyl versus Amino Substituents: Consequences on the Stability and Reactivity of Phosphanyl- and Aminocarbenes
✍ Scribed by Stéphanie Goumri; Yann Leriche; Heinz Gornitzka; Antoine Baceiredo; Guy Bertrand
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 145 KB
- Volume
- 1998
- Category
- Article
- ISSN
- 1434-1948
No coin nor oath required. For personal study only.
✦ Synopsis
Bis(diisopropylamino)(trimethylstannyl)phosphane (2) reacts the enamine 8 (92 % yield), while addition of sodium methoxide followed by thermolysis of the resulting with the (chloromethylene)diisopropylammonium salt 1 affording the C-phosphanyl-substituted iminium salt 3 (67 % hemiaminal 9 (90 % yield) gives rise to the azaphosphetane 10 (85 % yield), by intramolecular CH insertion of the yield), which features a short C-N (1.284 A ˚) and a long P-C bond (1.850 A ˚), a planar iminium nitrogen atom and a transiently formed (amino)(phosphanyl)carbene 6. pyramidalized phosphorus atom. Deprotonation of 3 leads to