Stereodivergent Synthesis of Carveol and Dihydrocarveol through Ketoreductases/Ene‐Reductases Catalyzed Asymmetric Reduction. Issue 23 (27th November 2018)

• Record Type: Journal Article
• Authors: Guo, Jiyang; Zhang, Rui; Ouyang, Jingping; Zhang, Feiting; Qin, Fengyu; Liu, Guigao; Zhang, Wenhe; Li, Hengyu; Ji, Xiaohong; Jia, Xian; Qin, Bin; You, Song
• Is Part Of: ChemCatChem. Volume 10:Issue 23(2018)
• Page Start: 5496
• Page End: 5504
• Publication Date: 2018-11-27
• Subjects: stereodivergent synthesis -- carveol -- dihydrocarveol -- ene-reductases -- ketoreductases -- asymmetric reduction; Catalysis -- Periodicals; 541.39505
• DOI: 10.1002/cctc.201801391
• Languages: English
• ISSNs: 1867-3880

Abstract

Abstract: 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. Abstract : Tasty, tasty : By directly asymmetric reduction of ( R )‐ and ( S )‐carvone using ketoreductases, all four possible stereoisomers of carveol with medium to high diastereomeric excesses (up to >99 %) were first observed. Then previously studied and newly engineered ene‐reductases were applied to synthesis four stereoisomers of dihydrocarvone. Asymmetric reduction of obtained dihydrocarvone isomers by ketoreductases further provide access to all eight stereoisomeric dihydrocarveol.