WestCHEM, School of Chemistry, The Joseph Black Building, University of Glasgow, Glasgow, UK G12 8QQ.
Org Biomol Chem. 2011 Apr 21;9(8):2801-8. doi: 10.1039/c0ob00619j. Epub 2011 Mar 2.
The stereoselective synthesis of a series of di- and tri-hydroxylated aminocyclohexane derivatives has been developed. A one-pot, two step tandem process involving an Overman rearrangement and a ring closing metathesis reaction has been utilised for the asymmetric synthesis of (1S)-1-(2',2',2'-trichloromethylcarbonylamino)cyclohexa-2-ene. Oxidation of this cyclohexene derivative was then studied leading to the preparation of two diol analogues in excellent stereoselectivity. (1S)-1-(2',2',2'-trichloromethylcarbonylamino)cyclohexa-2-ene was then converted to a novel allylic alcohol via a 4,5-dihydro-1,3-oxazole. Functionalisation of this allylic alcohol by Upjohn dihydroxylation conditions or by a directed epoxidation/hydrolysis sequence of reactions allowed the synthesis of two dihydroconduramines in excellent stereoselectivity. The stereochemical assignment of all compounds prepared was confirmed by NOE experiments or X-ray structure determination.
已经开发出一系列二羟基和三羟基氨基环己烷衍生物的立体选择性合成方法。采用一锅两步串联反应，包括 Overman 重排和环 closing metathesis 反应，用于（1S）-1-（2'，2'，2'-三氯甲基羰基氨基）环己-2-烯的不对称合成。然后研究了该环己烯衍生物的氧化，导致以优异的立体选择性制备了两种二醇类似物。（1S）-1-（2'，2'，2'-三氯甲基羰基氨基）环己-2-烯然后通过 4,5-二氢-1,3-恶唑转化为新型烯丙醇。通过 Upjohn 二羟基化条件或定向环氧化/水解反应序列对该烯丙醇进行官能化，允许以优异的立体选择性合成两种二氢康达明。通过 NOE 实验或 X 射线结构测定证实了所有制备化合物的立体化学构型。
