02410nas a2200193   4500008004100000245021700041210006900258260000800327300001400335490000800349520158300357100002401940700002201964700001901986700002502005700002502030700002302055856013802078       2011                        eng d00aCyclodiphosph(III)azane chemistry – ylides from the reaction of [(RNH)P-N(t-Bu)]2 [R = t-Bu, i-Pr] with dimethyl maleate and chiral ansa-type derivatives from reaction of [ClP-N(t-Bu)]2 with a substituted BINOL0 aCyclodiphosphIIIazane chemistry ylides from the reaction of RNHP  cJUN  a374–3820 v3723 a<p>Use of a simple inorganic ring system with the cyclodiphosph(III)azane skeleton [e.g. [(RNH)P-N(t-Bu)]2 [R = t-Bu (7), i-Pr (8)] to probe some of the intermediates proposed in phosphine mediated organic reactions is highlighted. Thus the reaction of 7–8 with the allenylphosphine oxide Ph2P(O)C(Ph)double bond; length as m-dashCdouble bond; length as m-dashCH2 (9) affords the phosphinimines [(RNH)P(μ-N-t-Bu)2P(double bond; length as m-dashN-R)-C(double bond; length as m-dashCH2)CH(Ph)-P(O)Ph2] [R = t-Bu (10), i-Pr (11)], while a similar reaction of 7–8 with dimethyl maleate (or dimethyl fumarate) affords the ylides [(RNH)P(μ-N-t-Bu)2P(NH-R)double bond; length as m-dashC(CO2Me)-CH2(CO2Me) [R = t-Bu (18), i-Pr (19)]. The implication of such reactions on phosphine mediated organic transformations including Morita–Baylis–Hillman reaction is mentioned. In a rather rare type of situation, an unusually long phosphoryl (Pdouble bond; length as m-dashO) bond [1.538 (5) Å] as revealed the X-ray structure of {(R)-6,6′-(t-Bu)2-1,1′-(C10H5)2-2,2′-O2-}{P(O)(N-t-Bu)2-P(Se)} (27) is rationalized by means of crystallographic disorder in packing after comparing the data with that in the literature and {1,1′-(C10H6)2-2,2′-O2}{P(Se)(N-t-Bu)2-P(Se)} (29). X-ray structures of the new compounds 10–11, 18–19, 27 and 29 are discussed. Compound 10 crystallizes in the chiral space group Pca2(1) with (S)-chirality at the carbon center [–C(double bond; length as m-dashCH2)CH(Ph)-P] suggesting a case of spontaneous resolution through crystallization.</p>1 aSwamy, K.C., Kumara1 aGangadhararao, G.1 aSrinivas, Venu1 aKumar, N., N. Bhuvan1 aBalaraman, Ekambaram1 aChakravarty, Manab  uhttps://library.ncl.res.in/content/cyclodiphosphiiiazane-chemistry-%E2%80%93-ylides-reaction-rnhp-nt-bu2-r-t-bu-i-pr-dimethyl-maleate