Organophosphorus Compounds; 141.~1 Phosphorus-Containing Cage Compounds from the Reaction of 7,8-Dichlorocycloocta-1,3,5-triene with tert-Butylphosphaacetylene and Subsequent Chemistry

摘要

tert-Butylphosphaacetylene (1) reacts at 120 deg C with the bicyclic form of cis-7,8-dichlorocycloocta-1,3,5-triene (11) in a Diels-Alder reaction to furnish the tricyclic product 12, whose constitution was confirmed by single crystal structure analysis of the corresponding #eta#~1-pentacarbonyltungsten complex 14. Compound 12 possesses a sterically fixed 1,4-diene system and fulfills the structural prerequisite for homo-Diels-Alder reactions, which can be realized with the electron-poor acetylenes 15 as well as the phos-phaacetylene 1 (-> 16, 20). Furthermore, the polycyclic systems 16 can be oxidized and complexed at the phosphorus atom (-> 18, 19).