Ring opening of a sterically crowded 1,2-oxaphosphetane complex

Abstract

The first example of a ring opening reaction of a 1,2-oxaphosphetane complex is reported, i.e., water in the presence of [Li(12-crown-4)]Cl furnished a C-OH functional phosphinito complex. Employment of the latter in ring forming reactions with MeECL (E = Si, Ge) using different nitrogen bases is also described.

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 .…”

Access to 1,1′‐Bifunctional Phosphane Iron(0) Complexes via P–N Bond‐Forming Reactions and Selective P‐Functionalizations

“…Taking this background into account, we recently envisaged a chance to broaden access to complexes V and, perhaps, also to VI using the versatile chemistry of Li/Cl phosphinidenoid complexes, in general, and the formal insertion reaction into N–H bonds in particular. In doing so, we were able to build up a versatile collection of secondary aminophosphanes while being coordinated to a transition metal fragment .…”

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).…”