Selenoether ligand assisted Heck catalysis

Tapash Chakraborty, Kriti Srivastava, Harkesh B. Singh, Ray J. Butcher

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22 Scopus citations

Abstract

Selenoether ligands, 2,2′-methylenebis(selanediyl)bis(2,1-phenylene) dimethanol (5), (2,2′-(ethane-1,2-diylbis(selanediyl))bis(2,1-phenylene)) dimethanol (6) and (2-(benzylselanyl)phenyl)methanol (7) have been synthesized by reducing di-o-formylphenyl diselenide and reacting the in situ generated selenolate with dibromomethane, 1,2-dibromoethane and benzyl chloride, respectively. The ligands, bis(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl) phenylselanyl)methane (8) and 1,2-bis(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl) phenylselanyl)ethane (9) have been synthesized similarly from bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide using electrophiles dibromomethane and 1,2-dibromoethane, respectively. Activity of ligands 5-9 along with 2-(2-(benzylselanyl)phenyl)-4,4-dimethyl-4,5-dihydrooxazole (10) and 1-(2-(benzylselanyl)phenyl)-N,N-dimethylmethanamine (11) were examined for the Heck reaction of aryl halides with olefins. Bidentate Se,N ligand 11 was found to be the best one in the series and constitutes an efficient phosphine-free catalytic system with PdCl2. The catalytic system showed moderate activity for the coupling of activated aryl chlorides in the presence of tetra-n-butyl ammonium bromide (TBAB). Complexes [10-PdCl2] (12) and [11-PdCl2] (13) have shown marginally better activity in comparison to the in situ generated catalysts from PdCl2 and 10 and 11, respectively in the coupling of 4-bromoacetophenone with n-butylacrylate. Ligand 9 and complex 13 have been characterized by single crystal X-ray diffraction analysis.

Original languageEnglish (US)
Pages (from-to)2559-2564
Number of pages6
JournalJournal of Organometallic Chemistry
Volume696
Issue number13
DOIs
StatePublished - Jul 1 2011

Bibliographical note

Funding Information:
We are thankful to the Department of Science and Technology (DST), India for funding this work. Additional help from the Sophisticated Analytical Instrument Facility (SAIF), Indian Institute of Technology, Bombay, for 300 MHz NMR spectroscopy is gratefully acknowledged. T. C. is also grateful to the Council of Scientific and Industrial Research, India for providing fellowship.

Keywords

  • Heck reaction
  • Palladium
  • Selenide
  • Selenoether

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