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New Intermediates in the Cyclocotrimerization of Thioxophosphorus( V ) Cations with Alkynes
Author(s) -
Lindner Ekkehard,
Käss Volker,
Hiller Wolfgang,
Fawzi Riad
Publication year - 1989
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198904481
Subject(s) - substituent , dimethyl acetylenedicarboxylate , chemistry , medicinal chemistry , hexane , stereochemistry , organic chemistry , catalysis , cycloaddition
A thiaphosphametallacyclopropane and a thiaphosphametallacycloheptadiene are important intermediates for understanding the mechanism of the cyclotrimerization of thioxophosphorus( V ) cations and alkynes. These species are accessible by use of a bulky substituent R at the phosphorus atom. Compounds 2 are formed from the metallacyclopropane 1 and dimethyl or diethyl acetylenedicarboxylate in hexane. Upon heating in THF, they lose CO and are transformed into the known metallabicycloheptadienes 3 . R 1 = cyclohexyl; R 2 = CO 2 Me, CO 2 Et.