Synthesis, Isolation, and Skeletal Inversion of 5,10-Dihydrophosphanthrenes

Abstract

Two stereoisomers, the trans form 1a and the cis form 1b, of 2,3,7,8-tetramethyl-5,10-diphenyl-5,10-dihydrophosphanthrene dioxide (1) were formed by spontaneous oxidation in air of the corresponding 5,10-dihydrophosphanthrenes 2 and were separated by recrystallization. Both 1a and 1b were characterized by X-ray crystallographic analysis, which revealed configurations at the phosphorus and conformations of the central tricyclic system. The ³¹P NMR of the reaction mixture showed at first two signals at −15.3 and −15.1 ppm, which shifted to 9.11 and 10.3 ppm after purification of the reaction mixture under aerobic conditions by oxidation of phosphorus atoms. The reaction of 1b with HSiCl₃ in toluene-d₈ at 100 °C gave no change, whereas 1a reacted with HSiCl₃ to give reduced compounds 2a and 2b under the same conditions. The trans–cis isomerization of 2 occurred via vertex inversion at phosphorus atom. VT-NMR, X-ray analysis, and density functional theory (DFT) calculation showed that the conformational exchange of the cis form 1b proceeded via skeletal inversion of the tricyclic ring.

Keywords:

• Isomerization
• skeletal inversion
• stereochemistry
• VT-NMR
• X-ray crystallographic analysis

Acknowledgments

This study was partially supported by a Grant-in-Aid for Encouragement of Young Scientists (B) to Y. U. (No. 16750041 and No. 18750037) from the Ministry of Education, Culture, Sports, Science and Technology of Japan and a Kitasato University Research Grant for Young Researchers.