02077nas a2200181   4500008004100000245010200041210006900143260000800212300001400220490000800234520140600242100002401648700002501672700002201697700002101719700002401740856013101764       2017                        eng d00aSynthesis of meta-substituted monodentate phosphinite ligands and implication in hydroformylation0 aSynthesis of metasubstituted monodentate phosphinite ligands and  cAUG  a1143-11520 v1293 aSynthesis of meta-substituted phosphinite ligands 3,3'-(methoxyphosphanediyl) bis(N, N-diethylaniline) (4a) and methoxybis(3-methoxyphenyl) phosphane (4b), in high yields, has been demonstrated. Typical phosphorus chemical shift between 110-120 ppm, appearance of methoxy protons and corresponding carbon, as well as ESI-MS spectra unambiguously confirmed the existence of phosphinite ligands 4a and 4b. To demonstrate the synthetic usefulness of 4a and 4b, these ligands were tested in the rhodium catalyzed hydroformylation of 1-octene. The diethylamine substituted ligand 4a was found to be highly active, whereas 4bwas less reactive but revealed slightly better regioselectivity of 62% under optimized conditions. Additionally, 4a and 4b were found to catalyze the hydroformylation of styrene, 1-undecenol and 1,1-disubstituted functional olefin, methyl methacrylate. Both the ligands displayed excellent conversion of styrene, and 4b revealed an excellent branch selectivity of 75%. Although 1-undecenol proved to be amenable to hydroformylation (85-90% conversion to aldehyde), both the ligands failed to discriminate between the linear and branched products. Substrate methyl methacrylate proved to be highly challenging and reduced conversion (between 33-42%) was observed under optimized conditions. Ligand 4a was found to be highly selective towards linear aldehyde (81% linear selectivity).1 aDeshmukh, Satej, S.1 aGaikwad, Shahaji, R.1 aPandey, Swechchha1 aMali, Pramod, S.1 aChikkali, Samir, H.  uhttps://library.ncl.res.in/content/synthesis-meta-substituted-monodentate-phosphinite-ligands-and-implication-hydroformylation