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Chemo-enzymatic preparation of copolymeric polythioesters containing branched-chain thioether groups

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Abstract

Branched-chain copolymeric polythioesters (PTE) were formed in good yield (∼87%) by chemoenzymatic reactions including thiyl radical-induced addition of 1,6-hexanedithiol to the >C=C< double bond of dimethyl 1,18-octadec-9-enedioate and transthioesterification of polyfunctional dimethyl 1,18-octadec-9-enedioate with bifunctional 1,6-hexanedithiol catalyzed by immobilized lipase from Rhizomucor miehei. The reactions were performed in vacuo at 80°C without a solvent. PTE was extracted from the reaction mixture using methyl-t-butylether and precipitated from i-hexane. The polymer structure of the i-hexane-insoluble PTE precipitate was elucidated by GPC/SEC showing an average molecular mass (M w) of 1,857 Da corresponding to a molecular weight range of up to 24,000 Da and a maximum degree of polymerization of up to 50 monomer units. Chemical derivatization with TMSH demonstrated the formation of up to ∼58 mol% of a branched-chain thio(S)ether, i.e., dimethyl S-9-(6-mercaptohexylthio)-1,18-octadecanedioate, and small proportions (∼8 mol%) of a dimeric disulfide formed therefrom. The chemical structures of various low-molecular weight (<900 Da) reaction products formed by transthioesterification, addition reaction or disulfide formation of the reactants or reaction intermediates, e.g., 1,18-octadec-9-enedioic acid methyl(O)ester 6′-S-mercaptohexyl thio(S)ester, dimethyl S-9-(6-mercaptohexylthio)-1,18-octadecanedioate, were elucidated by GC–MS. Similarly, dimethyl S-9-(6-S-methylthiohexylthio)-1,18-octadecanedioate and dimethyl 11,18,19,26-tetrathia-10,27-di-(7-carboxymethyl-heptyl)hexatriacontane-1,36-dioate were detected in the reaction mixtures after derivatization with trimethylsulfonium hydroxide.

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Acknowledgements

The authors wish to thank Dr. Kumar D. Mukherjee for valuable discussion.

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Correspondence to N. Weber.

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Fehling, E., Klein, E., Weber, N. et al. Chemo-enzymatic preparation of copolymeric polythioesters containing branched-chain thioether groups. Appl Microbiol Biotechnol 74, 357–365 (2007). https://doi.org/10.1007/s00253-006-0677-y

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Keywords

  • Branched-chain copolymeric polythioesters
  • Dimethyl 1,18-octadec-9-enedioate
  • 1,6-hexanedithiol
  • Immobilized lipase from Rhizomucor miehei (Lipozyme RM IM)
  • Transthioesterification