01889nas a2200181   4500008004100000022001400041245012600055210006900181260007100250300001400321490000700335520114600342100002201488700002101510700002401531700002401555856012801579       2015                        eng d  a0276-733300aHighly enantioselective Pd-catalyzed synthesis of P-stereogenic supramolecular phosphines, self-assembly, and implication0 aHighly enantioselective Pdcatalyzed synthesis of Pstereogenic su  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcOCT  a4802-48050 v343 a<p>Metal-catalyzed asymmetric addition of a secondary phosphine to an aryl halide is one of the most efficient and reliable approaches for the construction of enantiopure carbon phosphorus bonds. An isolated Pd(II) complex (5) catalyzes the carbon phosphorus coupling reaction between tolylphenylphosphine (la) and 3-iodophenylurea (2b), which proceeds with an unprecedented enantiomeric excess (ee) of 97%. The generality of the strategy has been demonstrated by preparing a small library of a new class of P-stereogenic phosphines with an in-built hydrogen bonding motif for the first time. The P-stereogenic phosphines self-assemble on a metal template via deliberately installed hydrogen-bonding motifs and mimic the bidentate ligand coordination. Interestingly, when it was employed in asymmetric hydrogenation, the supramolecular phosphine {1-(3-(phenyl(o-toly)phosphanyl)pheny)ureal} (6b) produced the corresponding hydrogenated product with the highest enantiomeric excess of 99% along with excellent conversion, demonstrating the potential of these enantioenriched P-chirogenic supramolecular phosphines in asymmetric catalysis.</p>1 aKoshti, Vijay, S.1 aMote, Nilesh, R.1 aGonnade, Rajesh, G.1 aChikkali, Samir, H.  uhttps://library.ncl.res.in/content/highly-enantioselective-pd-catalyzed-synthesis-p-stereogenic-supramolecular-phosphines-102517nas a2200205   4500008004100000245015200041210006900193260000800262300001600270490000700286520173400293100002102027700001702048700002302065700002502088700002202113700002402135700002402159856012802183       2017                        eng d00aH-Bonding assisted self-assembly of anionic and neutral ligand on metal: a comprehensive strategy to mimic ditopic ligands in olefin polymerization0 aHBonding assisted selfassembly of anionic and neutral ligand on   cOCT  a12448-124560 v563 aSelf-assembly of two neutral ligands on a metal to mimic bidentate ligand coordination has been frequently encountered in the recent past, but self-assembly of an anionic ligand on a metal template alongside a neutral ligand remains an elusive target. Such a self-assembly is hampered by additional complexity, wherein a highly negatively charged anion can form intermolecular hydrogen bonding with the supramolecular motif, leaving no scope for self-assembly with neutral ligand. Presented here is the self-association of anionic ligand 3-ureidobenzoic acid (2a) and neutral ligand 1-(3-(diphenylphosphanyl)phenyl)urea (1a) on a metal template to yield metal complex [{COOC6H4-NH(CO)NH2}{Ph2PC6H4NH(CO)NH2}PdMeDMSO] (4a). The identity of 4a was established by NMR and mass spectroscopy. Along the same lines, 3-(3-phenylureido)benzoic acid (2b) and 1-(3-(diphenylphosphanyl)phenyl)-3-phenylurea (1b) self-assemble on a metal template to produce palladium complex [{COOC6H4NH(CO)NHPh}{Ph2PC6H4NH(CO)NHPh}PdMePy] (5c). The existence of 5c was confirmed by Job plot, 1-2D NMR spectroscopy, deuterium labeling, IR spectroscopy, UV-vis spectroscopy, model complex synthesis, and DFT calculations. These solution and gas phase investigations authenticated the presence of intramolecular hydrogen bonding between hydrogen's of 1b and carbonyl oxygen of 2b. The generality of the supramolecular approach has been validated by preparing six complexes from four monodentate ligands, and their synthetic utility was demonstrated in ethylene polymerization. Complex 4a was found to be the most active, leading to the production of highly branched polyethylene with a molecular weight of 55700 g/mol and melting temperature of 112 degrees C.1 aMote, Nilesh, R.1 aPatel, Ketan1 aShinde, Dinesh, R.1 aGaikwad, Shahaji, R.1 aKoshti, Vijay, S.1 aGonnade, Rajesh, G.1 aChikkali, Samir, H.  uhttps://library.ncl.res.in/content/h-bonding-assisted-self-assembly-anionic-and-neutral-ligand-metal-comprehensive-strategy01881nas a2200157   4500008004100000022001500041245006200056210006200118260000800180300001400188490000700202520137200209100002101581700002401602856009701626       2018                        eng d  a 1861-472800aHydrogen bonding assissted supramolecular metal catalysis0 aHydrogen bonding assissted supramolecular metal catalysis  cDEC  a3623-36460 v133 aThe process of catalyst screening and discovery still largely relies on traditional ligand-design approaches, which suffer from complex synthetic requirements and offer limited structural diversity. On the contrary, supramolecular chemistry offers the potential to harness multiple weak secondary interactions to deliver self-assembled catalysts with diverse structures or to orient substrates to achieve enzyme-like activity and selectivity. Herein, the application of hydrogen-bonding (H-bonding) interactions as a construction element and directing group in "supramolecular transition-metal catalysis" is critically reviewed and the current state-of-the-art in the field is presented. H-bonding interactions empower structurally simple ligands to deliver complex self-assembled catalysts, which have been found to catalyze a gamut of organic transformations, including hydroformylation, hydrogenation, and allylation reactions. As we will discuss, on many occasions, these supramolecular catalysts outperform their analogous covalently linked catalytic systems. The potential of H-bonding interactions as directing groups has recently been recognized by the scientific community and this Focus Review presents the role of hydrogen-bonding interactions in directing substrates to obtain excellent selectivities and activities in a range of catalytic transformations1 aMote, Nilesh, R.1 aChikkali, Samir, H.  uhttps://library.ncl.res.in/content/hydrogen-bonding-assissted-supramolecular-metal-catalysis01877nas a2200157   4500008004100000022001500041245006100056210005900117260000800176300001400184490000700198520137300205100002101578700002401599856009601623       2018                        eng d  a1861-4728 00aHydrogen-bonding-assisted supramolecular metal catalysis0 aHydrogenbondingassisted supramolecular metal catalysis  cDEC  a3623-36460 v133 aThe process of catalyst screening and discovery still largely relies on traditional ligand-design approaches, which suffer from complex synthetic requirements and offer limited structural diversity. On the contrary, supramolecular chemistry offers the potential to harness multiple weak secondary interactions to deliver self-assembled catalysts with diverse structures or to orient substrates to achieve enzyme-like activity and selectivity. Herein, the application of hydrogen-bonding (H-bonding) interactions as a construction element and directing group in "supramolecular transition-metal catalysis" is critically reviewed and the current state-of-the-art in the field is presented. H-bonding interactions empower structurally simple ligands to deliver complex self-assembled catalysts, which have been found to catalyze a gamut of organic transformations, including hydroformylation, hydrogenation, and allylation reactions. As we will discuss, on many occasions, these supramolecular catalysts outperform their analogous covalently linked catalytic systems. The potential of H-bonding interactions as directing groups has recently been recognized by the scientific community and this Focus Review presents the role of hydrogen-bonding interactions in directing substrates to obtain excellent selectivities and activities in a range of catalytic transformations.1 aMote, Nilesh, R.1 aChikkali, Samir, H.  uhttps://library.ncl.res.in/content/hydrogen-bonding-assisted-supramolecular-metal-catalysis