01818nas 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

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.

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-account02223nas a2200253 4500008004100000022001400041245010100055210006900156260000800225300001100233490000800244520136700252653002401619653003201643653002201675653002901697653002101726653001801747100002101765700001901786700002401805700001701829856012301846 2023 eng d a0022-328X00aComputational insights into the iron-catalyze d magnesium-me diate d hydroformylation of alkynes0 aComputational insights into the ironcatalyze d magnesiumme diate cFEB a1226210 v9863 a

Iron is one of the most abundant transition metals in the earth's crust. It has attracted a lot of attention due to its low toxicity, bio-compatibility, and high natural abundance. Iron-catalyzed hydroamination, hydroalkoxylation, hydrocarboxylation, hydrosilylation, hydroboration, hydrophosphination, hydromagnesiation, and carbonylation reactions have therefore been developed over the past decades. However, despite many experimental and theoretical studies, a complete mechanistic understanding of iron-catalyzed hydrofunctionalisation at the molecular level has not yet been achieved. In this work, through density functional theory (DFT) calculations, we have shown the most feasible path for the hydroformylation of alkynes for an experimentally studied system. We have looked at the iron salt as a precatalyst without any external donor ligand, and the calculations revealed that hydrometalation followed by beta-hydride elimination was favorable over the direct migration of the beta-hydrogen to carbon. Furthermore, our calculations show that the solvent plays an important role in the hydromagnesiation reaction. Furthermore, we have employed an explicit solvent model, where the attachment of one molecule of solvent to the iron center was seen to stabilize the transition states significantly.(c) 2023 Elsevier B.V. All rights reserved.

10aComputational study10aEthylene Assisted Catalysis10aEtMgBr Assistance10aExplicit Role of Solvent10aHydroformylation10aIron Catalyst1 aSharma, Himanshu1 aTewari, Tanuja1 aChikkali, Samir, H.1 aVanka, Kumar uhttp://library.ncl.res.in/content/computational-insights-iron-catalyze-d-magnesium-me-diate-d-hydroformylation-alkynes01925nas a2200217 4500008004100000022001400041245008500055210006900140260000900209490000700218520122800225653001401453653001201467653001201479653002101491653001901512100001901531700001701550700002401567856011601591 2023 eng d a1867-388000aIron-catalyzed magnesium-mediated formal hydroformylation of alkynes and alkenes0 aIroncatalyzed magnesiummediated formal hydroformylation of alkyn cFEB 0 v153 a

Alkynes and alkenes are routinely converted to corresponding synthetically versatile aldehydes using rhodium-catalyzed hydroformylation. However, rhodium is rare, precious, costly, and depleting at a considerably high rate. Reported here is iron-catalyzed, magnesium-mediated, formal hydroformylation of alkynes and alkenes in the absence of syngas. Readily available FeCl2 in the presence of alkyl magnesium halide, and dimethyl formamide, catalyzes hydroformylation of various alkynes and selectively produces alpha,beta-unsaturated aldehydes in good to excellent conversion. Mechanistic investigations revealed the presence of vinyl magnesium intermediate, the kinetic study disclosed the first-order dependence of the reaction on iron loading, and the control experiment authenticated the iron catalyst's homogeneous nature. The scope of this methodology was amplified, and 20 alkenes were examined. [Fe(acac)(3)] in the presence of ligand, alkyl magnesium halide, and dimethyl formamide catalyzed the hydroformylation of alkenes and displayed good to excellent conversion. An earth-abundant iron catalyst offering a syngas cylinder-free safe alternative to high-pressure hydroformylation has been reported.

10aaldehydes10aalkenes10aAlkynes10aHydroformylation10airon catalysis1 aTewari, Tanuja1 aKumar, Rohit1 aChikkali, Samir, H. uhttp://library.ncl.res.in/content/iron-catalyzed-magnesium-mediated-formal-hydroformylation-alkynes-and-alkenes