18675-35-9Relevant articles and documents
From Bugs to Bioplastics: Total (+)-Dihydrocarvide Biosynthesis by Engineered Escherichia coli
Ascue Avalos, Gabriel A.,Toogood, Helen S.,Tait, Shirley,Messiha, Hanan L.,Scrutton, Nigel S.
, p. 785 - 792 (2019/01/29)
The monoterpenoid lactone derivative (+)-dihydrocarvide ((+)-DHCD) can be polymerised to form shape-memory polymers. Synthetic biology routes from simple, inexpensive carbon sources are an attractive, alternative route over chemical synthesis from (R)-carvone. We have demonstrated a proof-of-principle in vivo approach for the complete biosynthesis of (+)-DHCD from glucose in Escherichia coli (6.6 mg L?1). The pathway is based on the Mentha spicata route to (R)-carvone, with the addition of an ′ene′-reductase and Baeyer–Villiger cyclohexanone monooxygenase. Co-expression with a limonene synthesis pathway enzyme enables complete biocatalytic production within one microbial chassis. (+)-DHCD was successfully produced by screening multiple homologues of the pathway genes, combined with expression optimisation by selective promoter and/or ribosomal binding-site screening. This study demonstrates the potential application of synthetic biology approaches in the development of truly sustainable and renewable bioplastic monomers.
Stereodivergent Synthesis of Carveol and Dihydrocarveol through Ketoreductases/Ene-Reductases Catalyzed Asymmetric Reduction
Guo, Jiyang,Zhang, Rui,Ouyang, Jingping,Zhang, Feiting,Qin, Fengyu,Liu, Guigao,Zhang, Wenhe,Li, Hengyu,Ji, Xiaohong,Jia, Xian,Qin, Bin,You, Song
, p. 5496 - 5504 (2018/11/30)
Chiral carveol and dihydrocarveol are important additives in the flavor industry and building blocks in the synthesis of natural products. Despite the remarkable progress in asymmetric catalysis, convenient access to all possible stereoisomers of carveol and dihydrocarveol remains a challenge. Here, we present the stereodivergent synthesis of carveol and dihydrocarveol through ketoreductases/ene-reductases catalyzed asymmetric reduction. By directly asymmetric reduction of (R)- and (S)-carvone using ketoreductases, which have Prelog or anti-Prelog stereopreference, all four possible stereoisomers of carveol with medium to high diastereomeric excesses (up to >99 %) were first observed. Then four stereoisomers of dihydrocarvone were prepared through ene-reductases catalyzed diastereoselective synthesis. Asymmetric reduction of obtained dihydrocarvone isomers by ketoreductases further provide access to all eight stereoisomeric dihydrocarveol with up to 95 % de values. In addition, the absolute configurations of dihydrocarveol stereoisomers were determined by using modified Mosher's method.
Synthesis of optically active dihydrocarveol via a stepwise or one-pot enzymatic reduction of (R)- and (S)-carvone
Chen, Xi,Gao, Xiuzhen,Wu, Qiaqing,Zhu, Dunming
experimental part, p. 734 - 738 (2012/08/29)
A recombinant enoate reductase LacER from Lactobacillus casei catalyzed the reduction of (R)-carvone and (S)-carvone to give (2R,5R)-dihydrocarvone and (2R,5S)-dihydrocarvone with 99% and 86% de, respectively, which were further reduced to dihydrocarveols by a carbonyl reductase from Sporobolomyces salmonicolor SSCR or Candida magnolia CMCR. For (R)-carvone, (1S,2R,5R)-dihydrocarveol was produced as the sole product with >99% conversion, while (1S,2R,5S)-dihydrocarveol was obtained as the major product, but with a lower de when (S)-carvone was used as the substrate. The one-pot reduction was performed at a 0.1 M substrate concentration, indicating that it might provide an effective synthetic route to this type of chiral compound.