- A facile synthesis of catechol-functionalized poly(ethylene oxide) block and random copolymers
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Herein we develop a facile synthetic strategy for the functionalization of well-defined polyether copolymers with control over the number and location of catechol groups. Previously, the functionalization of polyethylene oxide (PEO)-based polymers with catechols has been limited to functionalization of the chain ends only, hampering the synthesis of adhesive and antifouling materials based on this platform. To address this challenge, we describe an efficient and high-yielding route to catechol-functionalized polyethers, which could allow the effects of polymer architecture, molecular weight, and catechol incorporation on the adhesive properties of surface-anchored PEO to be studied.
- Mattson, Kaila M.,Latimer, Allegra A.,McGrath, Alaina J.,Lynd, Nathaniel A.,Lundberg, Pontus,Hudson, Zachary M.,Hawker, Craig J.
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- Utilization of catecholic functionality in natural safrole and eugenol to synthesize mussel-inspired polymers
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Naturally occurring safrole I upon epoxidation gave safrole oxide II, which underwent ring opening polymerization using a Lewis acid initiator/catalyst comprising of triphenylmethylphosphonium bromide/triisobutylaluminum to afford new polyether III in excellent yields. Epoxy monomer II and allyl glycidyl ether IV in various proportions have been randomly copolymerized to obtain copolymer V. A mechanism has been proposed for the polymerization reaction involving chain transfer to the monomers. A strategy has been developed for the deprotection of the methylene acetal of V using Pb(OAc)4 whereby one of the methylene protons is replaced with a labile OAc group to give VI. The pendant allyl groups in VI have been elaborated via a thiol-ene reaction using cysteamine hydrochloride and thioglycolic acid to obtain cationic VII and anionic VIII polymers, both containing a mussel-inspired Dopa-based catechol moiety. During aqueous work up, the protecting group containing OAc was deprotected under mild conditions. Cationic VII and anionic VIII were also obtained via an alternate route using epoxide IX derived from 3,4-bis[tert-butyldimethylsilyloxy]allylbenzene. Monomer IX was homo- as well as copolymerized with IV using Lewis acid initiator/catalyst system to obtain homopolymer X and copolymer X1. Copolymer XI was then elaborated using a thiol-ene reaction followed by F- catalysed silyl deprotection to obtain mussel inspired polymers VII and VIII, which by virtue of having charges of opposite algebraic signs were used to form their coacervate.
- Alhaffar, Mouheddin T.,Akhtar, Mohammad N.,Ali, Shaikh A.
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p. 21265 - 21277
(2019/07/22)
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- Biomimetic synthesis of santalin a,b and santarubin a,b, the major colorants of red sandalwood
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Better late than never! Almost 200 years after Pelletier's pioneering studies on the chemical constituents of red sandalwood, the major santalins and santarubins have been synthesized. This efficient approach integrates a Knochel isoflavonoid synthesis with Friedel-Crafts allylations or olefin metatheses, and a final biomimetic reaction cascade that furnishes the venerable benzoxanthenone dyes in a single operation (see scheme). Copyright
- Strych, Sebastian,Trauner, Dirk
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p. 9509 - 9512
(2013/09/23)
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- Total synthesis of cimiracemate B and analogs
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The synthesis of the biologically active cimiracemate B and some analogs is described. The key step of the synthesis is a coupling between a bromoketone and a cinnamic acid derivative.
- Fache, Fabienne,Suzan, Nicolas,Piva, Olivier
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p. 5261 - 5266
(2007/10/03)
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