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

被引：47

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

共 50 条

[1] Chemoenzymatic Total Synthesis of Hydromorphone by an Oxidative Dearomatization/Intramolecular [4+2] Cycloaddition Sequence: A Second-Generation Approach
Rycek, Lukas
Hayward, John J.
Latif, Marwa Abdel
Tanko, James
Simionescu, Razvan
Hudlicky, Tomas
JOURNAL OF ORGANIC CHEMISTRY, 2016, 81 (22): : 10930 - 10941
[2] A formal total synthesis of securinine via an intramolecular [4+2] cycloaddition reaction
Honda, T
Namiki, H
Kudoh, M
Nagase, H
Mizutani, H
HETEROCYCLES, 2003, 59 (01) : 169 - 187
[3] A highly efficient total synthesis of (R)-(+)-muscopyridine by intramolecular [4+2] cycloaddition of bisketene
Suwa, Kie
Morie, Yasuko
Suzuki, Yumiko
Ikeda, Kiyoshi
Sato, Masayuki
TETRAHEDRON LETTERS, 2008, 49 (09) : 1510 - 1513
[4] Synthesis of isoindolinones: Intramolecular [4+2] cycloaddition/retro [4+2] of pyridone propiolamides
Wilson, Jonathan E.
Garvey, Joshua
Taveras, Kennedy M.
TETRAHEDRON LETTERS, 2019, 60 (41)
[5] Direct Dearomatization of Pyridines via an Energy-Transfer-Catalyzed Intramolecular [4+2] Cycloaddition
Ma, Jiajia
Strieth-Kalthoff, Felix
Dalton, Toryn
Freitag, Matthias
Schwarz, J. Luca
Bergander, Klaus
Daniliuc, Constantin
Glorius, Frank
CHEM, 2019, 5 (11): : 2854 - 2864
[6] The [4+2] Cycloaddition of 2-Pyrone in Total Synthesis
Cai, Quan
CHINESE JOURNAL OF CHEMISTRY, 2019, 37 (09) : 946 - 976
[7] Intramolecular [4+2] cycloaddition reactions of indolylalkylpyridazines:: synthesis of annulated carbazoles
Haider, N
Käferbock, J
TETRAHEDRON, 2004, 60 (31) : 6495 - 6507
[8] Regioselective Inter- and Intramolecular Formal [4+2] Cycloaddition of Cyclobutanones with Indoles and Total Synthesis of (±)-Aspidospermidine
Kawano, Mizuki
Kiuchi, Takaaki
Negishi, Shoko
Tanaka, Hiroyuki
Hoshikawa, Takaya
Matsuo, Jun-ichi
Ishibashi, Hiroyuki
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (03) : 906 - 910
[9] SYNTHESIS OF A NEW CONFORMATIONALLY DEFINED SEROTONIN HOMOLOG BY INTRAMOLECULAR [4+2] CYCLOADDITION
HERSLOF, M
MARTIN, AR
TETRAHEDRON LETTERS, 1987, 28 (30) : 3423 - 3426
[10] Studies on the synthesis of (±)-stenine:: A combined intramolecular [4+2]-cycloaddition/rearrangement cascade
Padwa, A
Ginn, JD
JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (13): : 5197 - 5206

← 1 2 3 4 5 →