02297nas a2200217   4500008004100000022001400041245013400055210006900189260000900258490000700267520147200274653002901746653002901775653002301804653001801827653002901845100002701874700002401901700002401925856013001949       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.  uhttps://library.ncl.res.in/content/thermally-stable-p-chiral-supramolecular-phosphines-their-self-assembly-and-implication-rh01640nas a2200229   4500008004100000022001400041245012500055210006900180260000900249300001100258490000700269520081400276653002901090653002601119653001801145653002001163653002401183100002701207700002401234700002401258856012801282       2026                        eng d  a2365-654900aDirect synthesis of phosphine-phosphite ligand and its implication in asymmetric hydrogenation of functionalized olefins0 aDirect synthesis of phosphinephosphite ligand and its implicatio  cFEB   ae075480 v113 a<p>
	Phosphine-phosphite (P-OP) ligands constitute a privileged class of chiral ligands in asymmetric catalysis owing to their modular structures and tunable steric and electronic properties. Herein, we report a direct, one-pot, synthesis of a new flexible P-OP ligand (L) derived from BINOL-PCl and its in situ complexation with rhodium (Rh) for catalytic evaluation. The resulting Rh/L system efficiently hydrogenates a diverse library of 19 functionalized olefins under mild conditions, delivering moderate to excellent enantioselectivities, with ee values reaching up to 99%. Several of the hydrogenated products correspond to valuable chiral building blocks relevant to pharmaceutical synthesis, underscoring the practical utility of flexible P-OP ligand architectures in asymmetric hydrogenation.</p>
10aasymmetric hydrogenation10afunctionalized alkene10aligand design10ametal catalyzed10aphosphine-phosphite1 aChandanshive, Amol, C.1 aKhopade, Kishor, V.1 aChikkali, Samir, H.  uhttps://library.ncl.res.in/content/direct-synthesis-phosphine-phosphite-ligand-and-its-implication-asymmetric-hydrogenation