Retrodienic reactions. Part 2. Vinyl- and propenyl-phosphines: synthesis by flash vacuum thermolysis and characterization

Abstract

The primary unsaturated phosphines, vinylphosphine (1 ), isopropenylphosphine (2) and ( E ) -prop-1enylphosphine (3) have been synthesized b y flash vacuum thermolysis of their formal Diels-Alder adducts with anthracene, cyclopentadiene, or 1,3-diphenyIisobenzofuran, obtained b y cycloaddition of these dienes with the corresponding dialkyl alkenylphosphonates, followed b y reduction with 1 it hi u m alumini u m hydride-c h lorotrimethylsilane. Compounds (1 )-( 3) were characterized from their spectral data and also as tungsten complex derivatives. The phosphines (1)-(3) exhibit a remarkable and unexpected stability [t; ca. 8 days for ( I ) and 5 days for (2) and (3)] under neutral conditions, in the dark, at room temperature, and were also observed by direct reduction of the corresponding phosphonates in tetrahydrofuran solution.

Allylation of Phosphorus, Arsenic, and Antimony Trihalides by Allylic Stannanes. Synthesis, Spectroscopic Characterization, and Quantum Chemical Investigations of Allylic Phosphines, Arsines, and Stibines

“…With LAH or Bu 3 SnH, the allylic phosphines 7a − f were obtained in good yields (≈80%) and exhibited a stability similar to those of vinylphosphines; they can be kept several weeks in pure form in a freezer (Scheme ). The allylic arsines 8a − f were obtained in a 70−75% yield.…”

Diels–Alder reactions of anthracene, 9-substituted anthracenes and 9,10-disubstituted anthracenes

“…67 Cycloaddition reactions of anthracene have been performed with unfunctionalised alkenes including C 60 , 68,69 C 60 F 18 70 and triphenylenetrisendoxides. 71 Although the reaction with triphenylenetrisendoxides only required reflux in xylene for 48 h to give modest yields of the adducts, the reaction with C 60 required heating the reactants under vacuum in a sealed tube at 2008C for 2 d to give 42% yield of the addition product.…”