Short Chemoenzymatic Total Synthesis of ent-Hydromorphone: An Oxidative Dearomatization/Intramolecular [4+2] Cycloaddition/ Amination Sequence**

被引：46

作者：

Varghese, Vimal ^{[1
,2
]}

Hudlicky, Tomas ^{[1
,2
]}

机构：

[1] Brock Univ, Dept Chem, St Catharines, ON L2S 3A1, Canada

[2] Brock Univ, Ctr Biotechnol, St Catharines, ON L2S 3A1, Canada

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 17期

基金：

加拿大创新基金会; 加拿大自然科学与工程研究理事会;

关键词：

alkaloids; cycloaddition; natural products; oxidation; total synthesis; ORTHO-BENZOQUINONE MONOKETALS; INTRAMOLECULAR DIELS-ALDER; FORMAL TOTAL-SYNTHESIS; ENANTIOSELECTIVE SYNTHESIS; EFFICIENT SYNTHESES; MORPHINE ALKALOIDS; RECENT PROGRESS; (-)-MORPHINE; STRATEGY; ADDUCTS;

D O I：

10.1002/anie.201400286

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A short synthesis of ent-hydromorphone has been achieved in twelve steps from -bromoethylbenzene. The key transformations involved the enzymatic dihydroxylation of the arene to the corresponding cis-dihydrodiol, Mitsunobu coupling with the ringA fragment, oxidative dearomatization of the C3 phenol, and the subsequent [4+2] cycloaddition to form ring B of the morphinan. The synthesis was completed by intramolecular amination at C9.

引用

页码：4355 / 4358

页数：4

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