A Convenient Method for the Synthesis of α‐Ethynylphospholes and Modulation of Their π‐Conjugated Systems

Abstract

Scheme 1. Synthesis of the silyl-capped a-ethynylphospholes 5 and 6.

Molecular Engineering of “Click”‐Phospholes Towards Self‐Assembled Luminescent Soft Materials

“…The deoxygenation of the oxides 3a‐O and 3b‐O could be achieved in relatively high yield (90–92%) by reaction with trichlorosilane in refluxing toluene. [10b] With the trivalent species in hand, we could then further modify the phosphorus center to evaluate the effect on the self‐assembly properties. Three typical modifications (gold‐complex formation, methylation, oxidation) were carried out to elaborate the potential reactivity of the trivalent phosphorus center ( Scheme ).…”

“…(a) Top: original ionic ‘phosphole‐lipid’ system; Bottom: current design strategy toward neutral phosphole‐lipids using a “click”‐phosphole; two conjugated heads ( a and b ) are used in this study. (b) Molecular structure of α‐alkynyl phospholes reported by Matano et al…”

“…It is expected that incorporation of a terminal alkynyl group into a phosphole system would generate highly valuable functional materials. However, the very few examples reported by Matano and co‐workers exclusively showcase α‐alkynyl phosphole systems (Scheme b) …”

Approach to the Synthesis of Five-Membered Organophosphorus Compounds via Alumoles and Alumolanes

“…A number of fairly effective approaches to the synthesis of cyclic OPCs include methods based on the direct conversion of five-membered metallacarbocycles based on transition metals into phosphocarbocycles using phosphorus dihalides. A few examples of the synthesis of phospholenes and phospholes from zirconacyclopentenes [7,8], zirconacyclopentadienes [9][10][11], and titanocyclopentadienes [12] are known in the literature. The direct conversion of aluminacarbocycles into cyclic OPCs has not been practically studied.…”