ISSN:
0947-6539
Keywords:
ab initio calculations
;
cyclic ylides
;
heterocycles
;
phosphorus ylides
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A number of possible strategies for the preparation of λ5-phosphetes were tested as follows: cyclopropenium 6 was treated with the lithium salt of diphenylphosphine to give phosphinocyclopropene 7, but 7 did not undergo ring expansion upon photolysis or thermolysis. P-chloro-C—trimethylsilyl-substituted ylide 8b reacted with two equivalents of dimethyl acetylenedicarboxylate to afford phosphinine 13 via a transient λ5-phosphete 12. Addition of aluminum trichloride to P-halogenated ylides 17a-b led to dihydrophosphetium salts 19a-b, which, upon treatment with pyridine, isomerized into the 1, 2-dihydrophosphet-2-ium salts 20a-b. Hydrolysis of derivatives 20a-b cleanly afforded phosphoniums 21 a-b, which reacted with NaN(SiMe3)2 to give rise to the corresponding λ5-phosphetes 22a-b. The benzo-λ5-phosphete 22a underwent ring expansion reactions with dimethyl acetylenedicarboxylate and acetonitrile, leading to benzo-λ5-phosphinine and benzo-1, 4λ5-azaphosphinine in good yields. Derivative 22b was characterized by X-ray crystal structure analysis. Ab initio SCF calculations, IGLO-13C chemical shifts and Δχ for various benzannulated derivatives and phosphorus heterocycles are presented.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19960020113
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