Direct Synthesis of Dibenzophospholes from Biaryls by Double C–P Bond Formation via Phosphenium Dication Equivalents

Abstract

We have developed a new strategy for the generation of phosphenium dication equivalents from readily available phosphinic acids and Tf 2 O. The in situ-generated dication equivalents can be readily coupled with simple (hetero)biaryls to form the corresponding dibenzophospholes directly. This protocol can also be applied to the concise synthesis of six-and seven-membered phosphacycles as well as the largely π-extended heteroacene derivatives, which are of great interest in the field of organic functional materials.

Thiophene‐Fused Naphthodiphospholes: Modulation of the Structural and Electronic Properties of Polycyclic Aromatics by Precise Fusion of Heteroles

“…On the other hand, the crystal structures of 2‐ cis and 3‐ cis exhibit slightly warped structures, which may be stemmed from the packing forces in the single crystals. The C−C and P−C bond lengths on the naphthodiphosphole core are comparable to those of reported naphthodiphosphole [23] . Thus, the positions of phosphole rings have negligible effect on their structural parameters.…”

“…The τ F values of 1 in CH 2 Cl 2 (1.1–1.5 ns) are smaller than those of 2 and 3 (2.0–2.9 ns). These values are similar to those of naphtho[2,3‐ b ]phosphole derivatives [23] . The radiative ( k r ) and nonradiative ( k nr ) rate constants are calculated from the values of τ F and Φ F .…”

“…The CÀ C and PÀ C bond lengths on the naphthodiphosphole core are comparable to those of reported naphthodiphosphole. [23] Thus, the positions of phosphole rings have negligible effect on their structural parameters.…”

“…These values are similar to those of naphtho[2,3b]phosphole derivatives. [23] The radiative (k r ) and nonradiative (k nr ) rate constants are calculated from the values of τ F and Φ F . The k r and k nr values for 2 and 3 are largely comparable.…”

Recent Advances in Luminescent Annulated Borepins, Silepins, and Phosphepins

“…Very recently, Hirano and Miura developed an elegant phosphenium dication equivalent method to synthesize benzophosphole-and benzothiophene-fused phosphepin 72 from benzophosphole 71 directly (Scheme 20). 42 Unfortunately, the photophysical and electrochemical chemistry of these two interesting phosphepins (70, 72) have not yet been investigated.…”