Regioselective and stereoselective alternating copolymerization of carbon monoxide with functional olefins

Abstract

Enantioselective, alternating copolymerizations of carbon monoxide with ω‐undecylenic acid, ethyl acrylate, and butyl acrylate were carried out for the first time with a palladium catalyst modified by 1,4:3,6‐dianhydro‐2,5‐dideoxy‐2,5‐bis(diphenylphosphino)‐L‐iditol. Optical rotation, elemental analysis, and 1H NMR,13C NMR, and IR spectra showed that the copolymers were optically active, isotactic, alternating poly(1,4‐ketone) or poly(spiroketal) structures. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2027–2036, 2001

Coordination−Insertion Copolymerization of Fundamental Polar Monomers

“…In contrast to the above-mentioned monomers, fundamental polar vinyl monomers whose polar group is directly attached to the olefin moiety are difficult to be copolymerized with CO . Among many problems associated with metal-catalyzed copolymerization of polar vinyl monomers with CO, the most critical one is formation of chelate intermediates after insertion of vinyl monomers.…”

Enantioselective Palladium-Catalyzed Transformations

“…Lu and co-workers have used a palladium catalyst modified by a 1,4,3,6-dianhydro-2,5-dideoxy-2,5-bis(diphenylphosphino)-l-iditol (DDPPI, 362 ) for the enantioselective copolymerization of α-olefins such as propene, heptene, 1-octene, and styrene as well as functionalized olefins such as ω-undecylenic acid, ethyl acrylate, and butyl acrylate (eq 115) …”

Undecylenic Acid: A Valuable and Physiologically Active Renewable Building Block from Castor Oil

“…[147,148] In fact, poly(spiroketal) structures 135 were formed, but after treatment with the acidic 1,1,1,3,3,3-hexafluoroisopropanol, poly(1,4-diketones) 136 were obtained.…”