Insertion of oxygen into carbon-phosphorus bonds of some strained phosphorus heterocycles

Template effects on the asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylphosphine and their arsenic elimination reaction

“…After 1 day, the Diels-Alder reaction product was found to be formed as observed from the 31 P{ 1 H} signal at d 37.7 which is identical to the value obtained for the enantiomerically pure version of the cycloadduct obtained as part of our previous studies involving DMPA and diphenylvinyphosphine albeit in that case the reaction was promoted by the chiral auxiliary [1]. Cyclic phosphine oxides with contracted internal C-P-C angles have been found to undergo oxygen insertion into a C-P bond [12,13]. The same phenomenon may occur in the cycloadduct resulting in oxygen being inserted into the As-C bond of the complex and thereafter, due to the inherent instability of such compounds, it results in a hydrolysis [12].…”

“…Cyclic phosphine oxides with contracted internal C-P-C angles have been found to undergo oxygen insertion into a C-P bond [12,13]. The same phenomenon may occur in the cycloadduct resulting in oxygen being inserted into the As-C bond of the complex and thereafter, due to the inherent instability of such compounds, it results in a hydrolysis [12]. Subsequently a Schenck ene reaction [14] caused double bond migration to a methyl group [15].…”

Synthesis and Properties of Phosphetanes

“…Yields are generally high, so that phosphetanes serve as practical precursors for 1,2-oxaphospholanes. 108,109 Insertion of nitrogen into various phosphetane rings has been performed through photolysis of the corresponding 1-azidophosphetane oxides in methanol (eq 35). [110][111][112] The main side products are ringopened methyl phosphonamidates.…”

“…155 Finally, the stereochemical outcome of the reduction of fused polycycles becomes difficult to predict, given the importance of ring strain in these reactions. 30,86,108 …”

Chemistry of the 2,3‐oxaphosphabicyclo[2.2.2]octene ring system: Extrusion of metaphosphates

“…Both types of 7-phosphanorbornene derivatives have proved to be remarkably sensitive to a reaction with peroxy acids, which smoothly accomplishes at room temperature the selective insertion of oxygen into a carbon-phosphoius bond. This type of reaction, first observed by Kashman [5], only occurs with cyclic phosphorus compounds where considerable contraction of the internal C-P-C bond (to 80-85") is present [6]. A plausible mechanism for the process is given in Scheme 2; support for the stereochemical result of retention at phosphorus will be presented later in this paper.…”