86. Tipker, R. M.; Muldoon, J. A.; Jo, J.; Connors, C. S.; Varga, B. R.; Hughes, R. P.; Glueck, D. S. Protonation of P-Stereogenic Phosphiranes: Phospholane Formation via Ring Opening and C–H Activation. ACS Omega 2023, 8, 12565–12572.

  

Abstract

Protonation of cyclopropanes and aziridines is well-studied, but reactions of phosphiranes with acids are rare, and have not been reported to result in ring opening. Treatment of syn-Mes*PCH₂CHR (Mes* = 2,4,6-(t-Bu)₃C₆H₂, R = Me or Ph, syn-1-2) or anti-Mes*PCH₂CHPh (anti-2) with triflic acid resulted in regiospecific anti-Markovnikov C-protonation with ring opening and cyclophosphination of a Mes* ortho-t-Bu group to yield the phospholanium cations [PH(CH₂CH₂R)(4,6-(t-Bu)₂-2-CMe₂CH₂C₆H₂)][OTf] (R = Me or Ph, 3-4), which were deprotonated with NEt₃ to give phospholanes 5-6. Enantioenriched or racemic syn-1 both gave racemic 3. The byproduct [Mes*PH(CH₂CH₂Me)(OH)][OTf] (7) was formed from syn-1 and HOTf in the presence of water. DFT calculations suggested that P-protonation followed by ring opening and hydride migration to C yields the phosphenium ion, [Mes*P(CH₂CH₂Me)][OTf], which undergoes C-H oxidative addition of an o-t-Bu methyl group. This work established a new reactivity pattern for phosphiranes.