ISSN:
1042-7163
Keywords:
Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Thermolysis of [bis(diisopropylamino)phosphanyl](trimethylsilyl)diazomethane 1 affords the corresponding carbene 2, which is stable enough to be spectroscopically characterized. This species possesses a phosphorus-carbon multiple-bond character as shown by the 2 + 3 and 2 + 2 cycloaddition reactions observed with trimethylsilyl azide or N2O and ethyl cyanoformate, respectively. On the other hand, 2 undergoes all the classical reactions of a carbene: cyclopropanation reaction with electron-poor alkenes, carbon-hydrogen bond insertion, and carbene-carbene coupling with isonitriles. Compound 2 reacts with trimethylsilyl triflate affording a stable methylenephosphonium salt 15. Treatment of the lithium salt of the [bis(diisopropylamino)thiophosphoranyl]diazomethane 18 with the bis(diisopropylamino)phosphanyl chloride leads to a stable nitrilimine 3. Thermolysis of 3 affords the isomeric diazo derivative 20, while photolysis gives rise to thiophophoranylnitrile 21 and cyclodiphosphazene 23. Regioselective 2 + 3 cycloadditions are observed with electron-poor dipolarophiles. Addition of trimethylsilyl triflate to 3 leads to a stable electrophilic nitrilimine 29.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hc.520020105
