Synthesis of meta-substituted monodentate phosphinite ligands and implication in hydroformylation

TitleSynthesis of meta-substituted monodentate phosphinite ligands and implication in hydroformylation
Publication TypeJournal Article
Year of Publication2017
AuthorsDeshmukh, SS, Gaikwad, SR, Pandey, S, Mali, PS, Chikkali, SH
JournalJournal of Chemical Sciences
Volume129
Issue8
Pagination1143-1152
Date PublishedAUG
Type of ArticleArticle
AbstractSynthesis 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).
DOI10.1007/s12039-017-1341-z
Type of Journal (Indian or Foreign)Indian
Impact Factor (IF)1.085
Divison category: 
Central NMR Facility
Polymer Science & Engineering

Add new comment