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  • Focus Review
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Chemoselective transesterification and polymer synthesis using a zincate complex

Abstract

In this focused review, I present an overview of our recent research on the zincate complex dilithium tetra-tert-butylzincate (TBZL)-catalyzed ring-opening polymerization (ROP) of ε-caprolactone, efficient acylation and transesterification of alcohols with vinyl acetate and carboxylic esters, and polymer synthesis with a high transesterification ability. In the first part of this report, the ROP of ε-caprolactone catalyzed by TBZL in toluene is described. In a subsequent study of the ROP of ε-caprolactone in the presence of 2-hydroxyethyl methacrylate (HEMA), TBZL was found to act not only as an anionic initiator but also as a transesterification catalyst. In the second part of this report, the acylation and transesterification of alcohols with vinyl acetate and carboxylic esters catalyzed by TBZL are summarized. The acylation proceeded quantitatively at 0 °C within 1 h. A wide range of combinations of esters and alcohols were suitable for the transesterification at 0 to −40 °C. In addition, the transesterification proceeded chemoselectively even in the presence of H2O and amines. Next, TBZL-catalyzed polycondensations of diphenyl carbonate (DPC) with diols are discussed. Irreversible polycondensations catalyzed by TBZL occurred to yield aliphatic polycarbonates under atmospheric pressure. In the last part of this report, the transesterifications of poly(phenyl methacrylate) (PPhMA) side chains with alcohols catalyzed by TBZL are described. The transesterification reaction not only with alkyl alcohols but also with fluoroalcohols occurred. By changing the reaction solvent and temperature, the degree of conversion could be controlled. The present system permits the partial, quantitative, or terminal conversion of polymethacrylates.

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References

  1. Kobayashi M, Matsumoto Y, Uchiyama M, Ohwada T. A new chemoselective anionic polymerization method for poly(N-isopropylacrylamide) (PNIPAm) in aqueous media: design and application of bulky zincate possessing little basicity. Macromolecules. 2004;37:4339–41.

    Article  CAS  Google Scholar 

  2. Uchiyama M, Kobayashi Y, Furuyama T, Nakamura S, Kajihara Y, Miyoshi T, et al. Generation and suppression of 3-/4-functionalized benzynes using zinc Ate Base (TMP−Zn−ate) :new approaches to multisubstituted benzenes. J Am Chem Soc. 2008;130:472–80.

    Article  CAS  Google Scholar 

  3. Furuyama T, Yonehara M, Arimoto S, Kobayashi M, Matsumoto Y, Uchiyama M. Development of highly chemoselective bulky zincate complex, tBu4ZnLi2: design, structure, and practical applications in small-/macromolecular synthesis. Chem Eur J. 2008;14:10348–56.

    Article  CAS  Google Scholar 

  4. Hirano T, Furutani T, Saito T, Segata T, Oshimura M, Ute K. Isotactic-specific anionic polymerization of N-isopropylacrylamide with dilithium tetra-tert-butylzincate in the presence of a fluorinated alcohol or Lewis acid. Polymer. 2012;53:4961–66.

    Article  CAS  Google Scholar 

  5. Labet M, Thielemans W. Synthesis of polycaprolactone: a review. Chem Soc Rev. 2019;38:3484–504. as a review

    Article  Google Scholar 

  6. Kitayama T, Yamaguchi H, Kanzawa T, Hirano T. Living ring-opening polymerization of ε-caprolactone with combinations of tert-butyllithium and bilky aluminium phenoxides. Polym Bull. 2000;45:97–104.

    Article  CAS  Google Scholar 

  7. Oshimura M, Okazaki R, Hirano T, Ute K. Ring-opening polymerization of ɛ-caprolactone with dilithium tetra-tert-butylzincate under mild conditions. Polym J. 2014;46:866–72.

    Article  CAS  Google Scholar 

  8. Oshimura M, Oda Y, Kondoh K, Hirano T, Ute K. Efficient acylation and transesterification catalyzed by dilithium tetra-tert-butylzincate at low temperatures. Tetrahedron Lett. 2016;57:2070–73.

    Article  CAS  Google Scholar 

  9. Nudelman A, Bechor Y, Falb E, Fischer B, Wexler BA, Nedelman A. Acetyl chloride-methanol as a convenient reagent for: A) quantitative formation of amine hydrochlorides B) carboxylate ester formation C) mild removal of N-t-BOC-protective group. Synth Commun.1998;28:471–4.

    Article  CAS  Google Scholar 

  10. Seebach D, Hungerbühler E, Naef R, Schnurrenberger P, Weidmann B, Züger M. Titanate-mediated transesterifications with functionalized substrates. Synthesis. 1982;2:138–41.

    Article  Google Scholar 

  11. Kim S, Lee JI. Copper ion promoted esterification of (S)-2-pyridyl thioates and 2-pyridyl esters. Efficient methods for the preparation of hindered esters. J Org Chem. 1984;49:1712–16.

    Article  CAS  Google Scholar 

  12. Otto MC. A simple, powerful, and efficient method for transesterification. J Chem Soc Chem Commun. 1986;9:695–7.

    Google Scholar 

  13. Taber DF, Amedio JC Jr, Patel YK. Selective benzoylation of diols with 1-(benzoyloxy)benzotriazole. J Org Chem. 1985;50:1751–2.

    Article  Google Scholar 

  14. Vedejs E, Bennett NS, Conn LM, Diver ST, Gringras M, Lin S, et al. Tributylphosphine-catalyzed acylations of alcohols: scope and related reactions. J Org Chem. 1993;58:7286–88.

    Article  CAS  Google Scholar 

  15. Grasa GA, Kissling RM, Nolan SP. N-heterocyclic carbenes as versatile nucleophilic catalysts for transesterification/acylation reactions. Org Lett. 2002;4:3583–86.

    Article  CAS  Google Scholar 

  16. Grasa GA, Güveli T, Singh R, Nolan SP. Efficient transesterification/acylation reactions mediated by n-heterocyclic carbene catalysts. J Org Chem. 2003;68:2812–19.

    Article  CAS  Google Scholar 

  17. Singh R, Kissling RM, Letellier M, Nolan SP. Transesterification/acylation of secondary alcohols mediated by N-heterocyclic carbene catalysts. J Org Chem. 2004;69:209–12.

    Article  CAS  Google Scholar 

  18. Nyce GW, Lamboy JA, Connor EF, Waymouth RM, Hedrick JL. Expanding the catalytic activity of nucleophilic N-heterocyclic carbenes for transesterification reactions. Org Lett. 2002;4:3587–90.

    Article  CAS  Google Scholar 

  19. Shirae Y, Mino T, Hasegawa T, Sakamoto M, Fujita T. ransesterification of various alcohols with vinyl acetate under mild conditions catalyzed by diethylzinc using N-substituted diethanolamine as a ligand. Tetrahedron Lett. 2005;46:5877–9.

    Article  CAS  Google Scholar 

  20. Mino T, Hasegawa T, Shirae Y, Sakamoto M, Fujita T. N,O-ligand accelerated zinc-catalyzed transesterification of alcohols with vinyl esters. J Organomet Chem. 2007;692:4389–96.

    Article  CAS  Google Scholar 

  21. Kwak H, Lee SH, Kim SH, Lee YM, Lee EY, Park BK, et al. Construction of ZnII compounds with a chelating 2,2’-dipyridylamine (Hdpa) ligand: anion effect and catalytic activities. Eur J Inorg Chem. 2008;3:408–15.

    Article  Google Scholar 

  22. Bosco JWJ, Agrahari A, Saikia AK. Molecular iodine-catalyzed selective acetylation of alcohols with vinyl acetate. Tetrahedron Lett. 2006;47:4065–8.

    Article  CAS  Google Scholar 

  23. Rathore PS, Advani J, Rathore S, Thakore S. Metal nanoparticles assisted amine catalyzed transesterification under ambient conditions. J Mol Catal A Chem. 2013;377:129–36.

    Article  CAS  Google Scholar 

  24. Lin MH, RajanBabu TV. Metal-catalyzed acyl transfer reactions of enol esters: role of Y5(OiPr)13O and (thd)2Y(OiPr) as transesterification catalysts. Org Lett. 2002;2:997–1000.

    Article  Google Scholar 

  25. Yoo DW, Han JH, Nam SH, Kim HJ, Kim C, Lee JK. Efficient transesterification by polymer-supported zinc complexes: clean and recyclable catalysts. Inorg Chem Commun. 2006;9:654–57.

    Article  CAS  Google Scholar 

  26. Oshimura M, Hirata T, Hirano T, Ute K. Synthesis of aliphatic polycarbonates by irreversible polycondensation catalyzed by dilithium tetra-tert-butylzincate. Polymer. 2017;131:50–5.

    Article  CAS  Google Scholar 

  27. Feng J, Zhuo RX, Zhang XZ. Construction of functional aliphatic polycarbonates for biomedical applications. Prog Polym Sci. 2012;37:211–36.

    Article  CAS  Google Scholar 

  28. Naik PU, Refes K, Sadaka F, Brachais CH, Boni G, Couvercelle JP, et al. Organo-catalyzed synthesis of aliphatic polycarbonates in solvent-free conditions. Polym Chem. 2012;3:1475–80.

    Article  CAS  Google Scholar 

  29. Park JH, Jeon JY, Lee JJ, Jang Y, Varghese JK, Lee BY. Preparation of high-molecular-weight aliphatic polycarbonates by condensation polymerization of diols and dimethyl carbonate. Macromolecules. 2013;46:3301–8.

    Article  CAS  Google Scholar 

  30. Wang L, Wang G, Wang F, Liu P. Transesterification between diphenyl carbonate and 1,6-hexandiol catalyzed by metal-organic frameworks based on Zn2+ and different aromatic carboxylic acids. Asian J Chem. 2013;25:5385–9.

    Article  CAS  Google Scholar 

  31. Wang Z, Yang X, Liu S, Hu J, Zhang H, Wang G. One-pot synthesis of high-molecular-weight aliphatic polycarbonates melt transesterification of diphenyl carbonate and diols using Zn(OAc)2 as a catalyst. RSC Adv. 2015;5:87311–9.

    Article  CAS  Google Scholar 

  32. Wang Z, Yang X, Li J, Liu S, Wang G. Synthesis of high-molecular-weight aliphatic polycarbonates from diphenyl carbonate and aliphatic diols by solid base. J Mol Catal A Chem. 2016;424:77–84.

    Article  CAS  Google Scholar 

  33. Fleischmann C, Anastasaki A, Gutekunst WR, McGrath AJ, Hustad PD, Clark PG, et al. Direct access to functional (meth)acrylate copolymers through transesterification with lithium alkoxides. J Polym Sci A Polym Chem. 2017;55:1566–74.

    Article  CAS  Google Scholar 

  34. Ito D, Ogura Y, Sawamoto M, Terashima T. Acrylate-selective transesterification of methacrylate/acrylate copolymers: postfunctionalization with common acrylates and alcohols. ACS Macro Lett. 2018;7:997–1002.

    Article  CAS  Google Scholar 

  35. Ohshima T, Iwasaki T, Maegawa Y, Yoshiyama A, Mashima K. Enzyme-like chemoselective acylation of alcohols in the presence of amines catalyzed by a tetranuclear zinc cluster. J Am Chem Soc. 2008;130:2944–5.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

I thank all of the colleagues and collaborators involved in this project. I especially express my sincere thanks to Prof. Koichi Ute and Assoc. Prof. Tomohiro Hirano (Tokushima University) for their assistance, valuable advice, and helpful discussions. This work was partially supported by a Grant-in-Aid for Young Scientists (B) of JSPS KAKENHI (No. 16K17915), Japan.

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Correspondence to Miyuki Oshimura.

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Oshimura, M. Chemoselective transesterification and polymer synthesis using a zincate complex. Polym J 53, 249–255 (2021). https://doi.org/10.1038/s41428-020-00416-4

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