02324nas a2200241   4500008004100000022001400041245010100055210006900156260006900225300001000294490000800304520143300312653001201745653003401757653002301791653003901814653001201853653002201865100001801887700002501905700002401930856012801954       2014                        eng d  a0010-854500aContemporary avenues in catalytic P-H bond addition reaction: a case study of hydrophosphination0 aContemporary avenues in catalytic PH bond addition reaction a ca  aPO BOX 564, 1001 LAUSANNE, SWITZERLANDbELSEVIER SCIENCE SAcAPR  a52-730 v2653 a<p>Remarkable advances and current state-of-the-art developments in catalytic hydrophosphination of alkenes and alkynes are reviewed. The challenges in constructing a C P bond with a special emphasis on metal catalysed (asymmetric) hydrophosphination are highlighted. Only those systems that unambiguously proceed via P H bond addition across a C-C/X (X = O, N, S) multiple bond have been covered in this overview. Reviewed examples support the assumption that either strongly chelating ligands or reaction products that act as ligands, enhance the rate of hydrophosphination. The asymmetric variant of this transformation allows installation of p-chiral [enantiomeric excess (ee) up to 82%] as well as C-chiral (ee up to 99%) centres. The limited spectroscopic, mechanistic data and OFT calculations point at two distinctly different mechanisms. In case of hydrophosphination, the metal undergoes oxidative addition and reductive elimination steps (in general), thus changing the oxidation state from M(0) to M(II) and back to M(0). Whereas in asymmetric hydrophosphination it is proposed that the oxidation state of the metal remains unaltered throughout the catalytic cycle. The examples described in this overview showcase the real power of catalytic hydrophosphination in constructing various phosphorus compounds, which may initiate a new era in organo-phosphorus chemistry. (C) 2014 Elsevier B.V. All rights reserved.</p>10aAlkynes10aAsymmetric hydrophosphination10aHydrophosphination10aMetal catalyzed hydrophosphination10aOlefins10aP-H bond addition1 aKoshti, Vijay1 aGaikwad, Shahaji, R.1 aChikkali, Samir, H.  uhttp://library.ncl.res.in/content/contemporary-avenues-catalytic-p-h-bond-addition-reaction-case-study-hydrophosphination-002036nas a2200289   4500008004100000022001400041245013000055210006900185260000800254300001400262490000700276520106100283653002601344653003101370653001201401653001401413653001701427100002501444700001701469700002401486700002101510700002701531700002401558700002101582700002401603856011901627       2020                        eng d  a2192-650600aPalladium-catalyzed insertion of ethylene and 1,1-disubstituted difunctional olefins: an experimental and computational study0 aPalladiumcatalyzed insertion of ethylene and 11disubstituted dif  cJUN  a1200-12090 v853 a<p>Insertion or coordination copolymerization of ethylene with di-substituted olefins is challenging and the choice of di-substituted mono-functional olefin versus di-substituted di-functional olefin (DDO) appears to be decisive. Here we show that DDO-inserted species are amenable to ethylene insertion and polymerization. DDOs such as 2-acetamidoacrylic acid (AAA), methyl 2-acetamidoacrylate (MAAA), and ethyl 2-cyanoacrylate (ECA) were treated with palladium complex [{P perpendicular to O}PdMe(L)] (P perpendicular to O=kappa(2)-P,O-Ar2PC6H4SO2O with Ar=2-MeOC6H4; L=C2H6OS) and the existence of respective insertion intermediates in moderate yield (up to 37 %) was established. These intermediates were exposed to ethylene and corresponding ethylene-inserted products were isolated and characterized. A careful comparison with three model compounds confirmed ethylene insertion and polymerization. Thus, the combined experimental and computational investigations show that DDO-inserted species can undergo ethylene insertion and polymerization.</p>
10aHomogeneous catalysis10ainsertion copolymerization10aOlefins10aPalladium10aPolyethylene1 aGaikwad, Shahaji, R.1 aPatel, Ketan1 aDeshmukh, Satej, S.1 aMote, Nilesh, R.1 aBirajdar, Rajkumar, S.1 aPandole, Satish, P.1 aChugh, Jeetender1 aChikkali, Samir, H.  uhttp://library.ncl.res.in/content/palladium-catalyzed-insertion-ethylene-and-11-disubstituted-difunctional-olefins