02052nas a2200277 4500008004100000022001400041245011600055210006900171260000800240300001500248490000900263520112800272653002901400653001401429653001901443653002201462653003101484100001701515700001701532700002201549700001501571700001701586700001701603700002401620856013001644 2022 eng d a1434-193X00aMechanistically guided one pot synthesis of phosphine-phosphite and its implication in asymmetric hydrogenation0 aMechanistically guided one pot synthesis of phosphinephosphite a cJAN ae2021014470 v20223 a
Although hybrid bidentate ligands are known to yield highly enantioselective products in asymmetric hydrogenation (AH), synthesis of these ligands is an arduous process. Herein, a one pot, atom-economic synthesis of a hybrid phosphine-phosphite (L1) is reported. After understanding the reactivity difference between an 0-nucleophile versus C-nucleophile, one pot synthesis of Senphos (L1) was achieved (72%). When L1 was treated with [Rh], P-31 NMR revealed bidentate coordination to Rh. Senphos, in the presence of rhodium, catalyzes the AH of Methyl-2-acetamido-3-phenylacrylate and discloses an unprecedented turn over frequency of 2289, along with excellent enantio-selectivity (92%). The generality is demonstrated by hydrogenating an array of alkenes. The AH operates under mild conditions of 1-2 bar H-2 pressure, at room temperature. The practical relevance of Ll is demonstrated by scaling-up the reaction to 1 g and by synthesizing DOPA, a drug widely employed for the treatment of Parkinson's disease. Computational insights indicate that the R isomer is preferred by 3.8 kcal/mol over the S isomer.
10aasymmetric hydrogenation10acatalysis10aDOPA synthesis10aOne pot synthesis10aPhosphine-phosphite ligand1 aSen, Anirban1 aKumar, Rohit1 aPandey, Swechchha1 aRaj, Vipin1 aKumar, Pawan1 aVanka, Kumar1 aChikkali, Samir, H. uhttp://library.ncl.res.in/content/mechanistically-guided-one-pot-synthesis-phosphine-phosphite-and-its-implication-asymmetric