01721nas a2200241   4500008004100000022001400041245011000055210006900165260000800234300000800242490000800250520087600258653002501134653002001159653001701179653002801196653002701224100002501251700002701276700002101303700002401324856013101348       2021                        eng d  a0974-362600aNi-catalyzed highly enantioselective synthesis of sulfur protected P-stereogenic supramolecular phosphine0 aNicatalyzed highly enantioselective synthesis of sulfur protecte  cDEC  a1190 v1333 aAs phosphines readily invert, the synthesis of P-chiral phosphines is a challenging task and has been rarely investigated. We report the synthesis of a nickel complex [Ni-((S,S)Me-FerroLANE)(phenyl)(I)] (Ni-Cat.1) and its performance in a P-C coupling reaction to generate P-chiral phosphine. The Ni-Cat.1 was synthesized by mixing ligand (S,S) Me-FerroLANE with the metal precursor [(diphenylphosphanyl)nickel(phenyl)(I)] in good yield. Ni-Cat.1 was characterized using different spectroscopic and analytical techniques. Treatment of racemic methyl(phenyl)phosphine (1) with 1-(3-iodophenyl)urea (2) produced the corresponding P-chiral supramolecular phosphine (3). Optimization of reaction parameters produced sulfur protected phosphine N-(3-(methyl(phenyl)phosphorothioyl)phenyl)formamide (3') with excellent enantiomeric excess (99% ee) and moderate conversion (51%).10aAsymmetric synthesis10aNickel catalyst10aP-C coupling10aP-Stereogenic phosphine10asupramolecular ligands1 aKoshti(S), Vijay, S.1 aChandanshive, Amol, C.1 aMote, Nilesh, R.1 aChikkali, Samir, H.  uhttp://library.ncl.res.in/content/ni-catalyzed-highly-enantioselective-synthesis-sulfur-protected-p-stereogenic-supramolecular01818nas a2200217   4500008004100000022001400041245008100055210006900136260000800205520109100213653002601304653002101330653001801351653001201369653002301381100001901404700001701423700002701440700002401467856010901491       2021                        eng d  a1527-899900aPhosphorus ligands in hydroformylation and hydrogenation: a personal account0 aPhosphorus ligands in hydroformylation and hydrogenation a perso  cMAR3 a<p>Metal-catalyzed hydroformylation and hydrogenation heavily rely on ligands, among which phosphorous ligands play a pivotal role. This personal account presents a selection of three distinct classes of phosphorous ligands, namely, monodentate meta-substituted phosphinites, bis-phosphites, and P-chiral supramolecular phosphines, developed in our group. The synthesis of these ligands, isolation, characterization, and their performance in transition metal-catalyzed hydroformylation, isomerizing hydroformylation, and asymmetric hydrogenation of olefins is summarized. The state of the art development in iron-catalyzed hydroformylation of alkenes and our contributions to the field is discussed. Use of phosphines enabled iron-catalyzed hydroformylation of alkenes under mild conditions. Thus, this account demonstrates the central role of phosphorus ligands in industrially relevant transformations such as hydrogenation and hydroformylation. The seemingly matured field of ligand discovery still holds significant potential and will steer the field of homogeneous catalysis.</p>
10aHomogeneous catalysis10aHydroformylation10aHydrogenation10aOlefins10aPhosphorus ligands1 aTewari, Tanuja1 aKumar, Rohit1 aChandanshive, Amol, C.1 aChikkali, Samir, H.  uhttp://library.ncl.res.in/content/phosphorus-ligands-hydroformylation-and-hydrogenation-personal-account02296nas a2200217   4500008004100000022001400041245013400055210006900189260000900258490000700267520147200274653002901746653002901775653002301804653001801827653002901845100002701874700002401901700002401925856012901949       2024                        eng d  a0947-653900aThermally stable P-chiral supramolecular phosphines, their self-assembly and implication in Rh-catalyzed asymmetric hydrogenation0 aThermally stable Pchiral supramolecular phosphines their selfass  cAUG 0 v303 a<p>
	P-chiral supramolecular phosphine ligands are crucial for asymmetric transformations, but their synthesis is tedious. We report a one-step synthesis of thermally stable P-chiral supramolecular phosphines and their performance in the asymmetric hydrogenation of functionalized alkenes. A rational designing and synthesis of (R, R)-QuinoxP* ligated palladium complex (Pd-2) in excellent yield is reported. This Pd-2 catalyzed a direct P-C coupling of 2,3-dihydro-1-H-phosphindole (A1)/1,2,3,4-tetrahydrophosphindoline (A2) with 1-(3-iodophenyl)urea (B1)/2-iodo /6-hydroxy pyridine (B2) and,produced corresponding ligands L1-L3. The P-C coupling between A1 and B2 produced 6-(2,3-dihydro-1H-phosphindol-1-yl)pyridine-2(1H)-one (L2) with an excellent enantiomeric excess of up to 99 %. L2 was found to be remarkably stable even at 150 degrees C and did not oxidize/hydrolyze for at least 24 hours in open air. Such thermal stability and an impediment to oxidation are unprecedented. L2 self-assembled and produced L2-C1 (Pt), L2-C2(Pd), and L2-C3(Rh) assemblies. The utility of the self-assembled P-chiral ligand was demonstrated in the Rh-catalyzed asymmetric hydrogenation (AH) of functionalized olefins. The L2-C3 catalyzed AH of functionalized alkenes and delivered chiral products with excellent enantioselectivity of &gt;99 %. A small library of 16 substrates was subjected to AH using L2-C3 to produce chiral compounds with excellent conversion and ee.</p>
10aasymmetric hydrogenation10aAsymmetric phosphination10aP-chiral phosphine10aSelf-assembly10aSupramolecular phosphine1 aChandanshive, Amol, C.1 aGonnade, Rajesh, G.1 aChikkali, Samir, H.  uhttp://library.ncl.res.in/content/thermally-stable-p-chiral-supramolecular-phosphines-their-self-assembly-and-implication-rh