Photoinduced Syntheses and Reactivities of Phosphorus-Containing Interelement Compounds

Abstract

The photoinduced reactions of tetraphenyldiphosphine disulfide with a range of organic dichalcogenides successfully afforded a series of phosphorus(V)−chalcogen interelement compounds via a radical process. The relative reactivities of the organic dichalcogenides (i.e., (PhS) 2 , (PhSe) 2 , and (PhTe) 2 ) toward the P III or P V groups in the diphosphine analogues under light were investigated in detail, and a convenient method was developed to form P−S or P−Se interelement compounds from tetraphenyldiphosphine disulfide and (PhS) 2 or (PhSe) 2 upon photoirradiation. Furthermore, the relative photochemical properties and reactivities of tetraphenyldiphophine (P− P interelement compound) and its analogues toward photoinduced radical addition reactions were also discussed. The formed P−E (E = S, Se) interelement compounds could be utilized for ionic reactions, and they could be transformed into various phosphine reagents via one-pot processes.

Metal-Free One-Pot Multi-Functionalization of Unsaturated Compounds with Interelement Compounds by Radical Process

“…The P V –Ch bond formation usually proceeds via ionic pathways, using air- and moisture-sensitive reagents, and there has been no example of a radical method for the preparation of P V –Ch bonds. Therefore, the developed method will contribute to the further utilization of phosphorus-centered interelement compounds in organic synthesis [ 66 ].…”

Photoinduced Synthesis of Bisphosphinated Quinoxalines via Radical Cyclization ofo‐Diisocyanoarenes with Diphosphines

“…Thus, we previously investigated the photoinduced reaction of 2‐alkynylphenyl isocyanide 1 a with diphenyl dichalcogenides ((PhE) 2 , E=S, Se, Te) [4] . The desired bisthiolative cyclization of 1 a with (PhS) 2 did not proceed at all due to inefficient homolysis of (PhS) 2 by the irradiation with the light of wavelength above 300 nm (λ max of (PhS) 2 =250 nm [5] ) or lower carbon radical trapping ability of (PhS) 2 ( k S =7.6×10 4 M −1 s −1 ) [6] (eq. .…”

“…In sharp contrast, (PhSe) 2 and (PhTe) 2 reacted successfully with 1 a to afford 2,4‐bisselenated and 2,4‐bistellurated quinolines 2 b and 2 c , respectively, in good yields. This is owing to the efficient homolysis of (PhSe) 2 and (PhTe) 2 (λ max of (PhSe) 2 and (PhTe) 2 =354 nm and 406 nm [5] ) and the higher carbon radical trapping ability of (PhSe) 2 and (PhTe) 2 ( k Se =1.2×10 7 M −1 s −1 and k Te =4.8×10 7 M −1 s −1[6] ).…”

Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization

“…The radical addition reactions of halogens and organic disulfides have been reported to occur under photoirradiation, but their synthetic applications are limited. To clarify the universality of the photoinduced radical reaction of heteroatom compounds as a method for generating carbon-heteroatom bonds, we previously investigated a series of radical addition reactions to the carbon-carbon unsaturated bonds, of group 16 (e.g., diselenides and ditellurides) [32][33][34][35][36], group 15 (e.g., diphosphines) [37][38][39][40][41][42], and group 13 (e.g., diboranes) compounds [43,44]. We then combined these reactions with disulfides and fluorinated iodoalkanes and successfully formed a variety of carbon-heteroatom bonds [45][46][47][48][49][50][51][52][53].…”