Lipase-mediated regioselective modifications of macrolactonic sophorolipids

TETRAHEDRON

卷:73

Article

Sembayeva, Aliya¹  Berhane, Beniam²  Carr, Jason A.¹ 

[1] Nazarbayev Univ, Dept Chem, 53 Kabanbay Batyr Ave, Astana 010000, Kazakhstan

[2] Univ Calif Irvine, Dept Chem, Nat Sci 2 1102, Irvine, CA 92697 USA

关键词: Sophorolipids;    Glycolipids;    Lipases;    NMR spectroscopy;    Lactone;    Fatty acid esters;    Biosurfactant;   

DOI  :  10.1016/j.tet.2017.02.043

来源: Elsevier

【 摘 要 】

Chemoenzymatic synthesis and modification of well-defined macrolactonic sophorolipid (SLML) analogues via a series of successive regioselective de-esterification/transesterification reactions is investigated. Of the lipases screened, Candida antartica lipase- B (Novozyme-435) successfully deacylated the C-6' acetoxy group of natural and peracylated SLMLs. Subsequent transesterification with acylating agents (esters of fatty acids) was successful only with the C-6' deacetylated natural SLML providing an avenue to well-defined analogues of varying amphilicity. The macrolactonic motif was essential for enzymatic recognition of the sophorose rings of these complex glycolipids. In the absence of the lactonic motif, the peracylated sophorose rings are not deacylated, rather the carboxyl end of the non-lactonic forms that was preferentially transesterified. All macrolactonic derivatives were characterized by IR, H-1, C-13, H-1-H-1 and H-1-C-13 NMR spectroscopy, as well as HRMS where applicable. (C) 2017 Elsevier Ltd. All rights reserved.

【 授权许可】

Free