Organic and Biomolecular Chemistry p. 77 - 88 (2017)
Update date:2022-08-17
Topics:
Osorio-Nieto, Urbano
Vázquez-Amaya, Laura Y.
H?pfl, Herbert
Quintero, Leticia
Sartillo-Piscil, Fernando
The substrate-controlled asymmetric total synthesis and absolute configurational assignment of biologically active 3α,4α-epoxy-5β-pipermethystine, a minor component in the aerial parts of kava, has been achieved by featuring, as a key step, the environmentally friendly and direct synthesis of 2,3-epoxyamides from allyl amines. By using the chiron approach, first a carbohydrate-derived dehydropiperidine was prepared and subjected to a stereoselective tandem C-H/CC oxidation reaction. In this attempt, the required α,α-trans-epoxy-2-piperidone skeleton of the kava metabolite precursor was not achieved, although the tandem oxidation was highly stereoselective. However, starting from non-carbohydrate 3-hydroxy-4,5-dehydropiperidine, and using the same tandem oxidation, the target intermediate was obtained in high yield and complete unprecedented anti-stereoselectivity. Since the proposed mechanistic course of this tandem oxidation implies the transient formation of an α,β-unsaturated amide followed by the subsequent epoxidation reaction, this second approach supports the previously established biotransformation proposal of (-)-pipermethystine to (-)-3α,4α-epoxy-5β-pipermethystine.
View MoreChangZhou XiaQing Chemical Co., Ltd.
Contact:+86-519-88721665
Address:3# Hengluo Road, Henglin Town, Changzhou City, Jiangsu Province,China
Hangzhou GreenCo Science & Technology Co., Ltd.
Contact:86-571-88257303
Address:1713 Room,Jingui Building,Gudun Road,Xihu District,Hangzhou,China
JIANGXI AIFEIMU TECHNOLOGY CO.,LTD
Contact:+86-570-6040289
Address:FINECHEMICAL PARK,ZIBU TOWN,WANNIAN COUNTY,JIANGXI PROV.,CHINA,ZIP
Shanghai Longjin Metallic Material Co., Ltd.
website:http://www.shlongjin.cn/
Contact:021-56517503,56502257
Address:No.16, Lane 555, Chengyin Road, Shanghai
Jiangsu Willing Bio-Tech Co ltd
website:http://www.willingbio.com/
Contact:+86 18796909136
Address:No 18 Guoqiao Road
Doi:10.1002/asia.201300400
(2013)Doi:10.14233/ajchem.2014.18504
(2014)Doi:10.1021/ja01072a026
(1964)Doi:10.1021/bi00682a021
(1975)Doi:10.1002/jps.23050
(2012)Doi:10.1063/1.1725240
(1964)