A novel route to C-unsubstituted 1,2-oxaphosphetane and 1,2-oxaphospholane complexes

Abstract

The synthesis of 1,2-oxaphosphetane complexes and 1,2-oxaphospholane complex bearing only substituents at phosphorus is reported using the reaction of Li/Cl phosphinidenoid complex with 2-iodoethanol or 3-bromo-propane-1-ol and the subsequent dehydrohalogenation using KHMDS. In contrast, the reaction of complex with (t)BuLi leads selectively to the formation of phosphinito complex .

Oxophosphonium-alkyne cycloaddition reactions: reversible formation of 1,2-oxaphosphetes and six-membered phosphorus heterocycles

“…Given the importance of 1,2σ 5 λ 5 -oxaphosphetanes C as intermediates in the Wittig reaction , and the rich chemistry of 1,2σ 3 λ 3 -oxaphosphetanes B developed by the group of Streubel, − it is surprising that 1,2-oxaphosphetes have not yet been isolated. Keglevich and co-workers postulated 1,2σ 5 λ 5 -oxaphosphete intermediates in the reaction of phosphine oxides with the particularly electrophilic alkyne dimethylacetylenedicarboxylate .…”

Addressing the Nature of Phosphinidene Sulfides via the Synthesis of P−S Heterocycles

“…In this particular case, structural characterization of the first 1,2-oxaphosphetane [1] and NMR spectroscopic data [2] favoured the formation of the strained 4-membered PÀOh eterophosphete. [3][4][5][6][7][8][9] Although chemistry of the 1,2-oxaphosphetanes, either containing transition-metal stabilized P III (A) [10][11][12][13] or pentavalent phosphorus (B) [14][15][16][17] have been studied, the heavierc halcogen derivativesa re considerably underdeveloped in comparison. The most common examples of heterophosphetes containing heavierc halcogens are 1,2-thiaphosphetanes, which containa saturated 4-membered PSC 2 ring and ap entavalentp hosphorus atom (C & D).…”

“…The photolysis of 4 appearst ob e au nique methodo fu tilizing an indefinitely stable P V -centered compound as as toichiometrics ource of P III -S, by leveraging to the extrusion of the monomeric Ar*P=S, which is consistent with what has been reportedf or the fully saturated phosphirane sulfide derivatives. [24] (11). 4b:P(1)ÀS(1) 1.9443 (7), P(1)ÀC(1) 1.8176 (14), P(1)ÀC(25) 1.7684 (14), P(1)ÀC(26) 1.7561 (14), C(25)ÀC (26) As an alternative to thermolysis of dithiadiphosphetane (1) as ap recursor to Ar*P=Sand ultimately compounds 3 or 4,the direct 1:1a ddition of compounds 5 and 6 (Scheme 3) in the presence of excessp henylacetylene at room temperature resulted in 4a being the only P-S heterocycle formed as indicated by 31 P{ 1 H} NMR spectroscopy.T his route also leads to an improvedo verall yield in comparison to thermolysis (44 % yield).…”

1,2σ3λ3-Oxaphosphetanes and Their P-Chalcogenides—A Combined Experimental and Theoretical Study

“…In contrast, only the low-coordinate 1,2σ 3 λ 3 -oxaphosphetanes ( IVa ) were proposed [ 19 ] for a long time, with no stable derivative known. We synthesized the corresponding κP -pentacarbonylmetal(0) complexes (M = Cr, Mo, W) ( V ) either through ring expansion of epoxides using highly reactive phosphinidenoid complexes [ 20 , 21 ], or ring formation through intramolecular nucleophilic attack. Recently, the free ligand was obtained [ 22 ] using a decomplexation strategy [ 23 ] for octahedral complexes [M(CO) 5 L] by a combined thermal substitution with the chelating effect of bis(diphenylphosphino)ethane (DPPE).…”