76-80-2Relevant articles and documents
General Synthetic Approach to Rotenoids via Stereospecific, Group-Selective 1,2-Rearrangement and Dual S N Ar Cyclizations of Aryl Fluorides
Matsuoka, Seiya,Nakamura, Kayo,Ohmori, Ken,Suzuki, Keisuke
, p. 1139 - 1156 (2019/02/26)
A general synthetic approach to rotenoids is described, featuring 1) stereospecific, group-selective 1,2-rearrangements of epoxy alcohols, and 2) S N Ar oxy-cyclizations of aryl fluorides. The common intermediate epoxyketone, en route to (-)-rotenone and (-)-deguelin, was prepared from d -araboascorbic acid in five steps. Also described is the conversion of (-)-deguelin into oxidized congeners, (-)-tephrosin and (+)-12a- epi -tephrosin.
Concise Total Synthesis of (±)-Deguelin and (±)-Tephrosin Using a Vinyl Iodide as a Key Building Block
Xu, Shengtao,Wang, Guangyu,Xu, Feijie,Li, Wenlong,Lin, Aijun,Yao, Hequan,Xu, Jinyi
, p. 1055 - 1059 (2018/05/07)
A concise and protecting-group-free total synthesis of the antiproliferative natural product (±)-deguelin (2) was accomplished in four steps and 62% overall yield from commercially available precursors. The key transformation employed a vinyl iodide as the pivotal building block to construct the 4-acylchromene substructure present in deguelin. Subsequent Cu2O-mediated α-hydroxylation of deguelin (2) afforded tephrosin (3) in 90% yield.
Stereocontrolled semi-syntheses of deguelin and tephrosin
Russell, David A.,Freudenreich, Julien J.,Ciardiello, Joe J.,Sore, Hannah F.,Spring, David R.
supporting information, p. 1593 - 1596 (2017/02/23)
We describe stereocontrolled semi-syntheses of deguelin and tephrosin, anti-cancer rotenoids isolated from Tephrosia vogelii. Firstly, we present a new two-step transformation of rotenone into rot-2′-enonic acid via a zinc-mediated ring opening of rotenone hydrobromide. Secondly, following conversion of rot-2′-enonic acid into deguelin, a chromium-mediated hydroxylation provides tephrosin as a single diastereoisomer. An étard-like reaction mechanism is proposed to account for the stereochemical outcome. Our syntheses of deguelin and tephrosin are operationally simple, scalable and high yielding, offering considerable advantages over previous methods.
Concise modular asymmetric synthesis of deguelin, tephrosin and investigation into their mode of action
Garcia, Jose,Barluenga, Sofia,Beebe, Kristin,Neckers, Len,Winssinger, Nicolas
body text, p. 9767 - 9771 (2010/10/21)
(Figure Presented) The concise nature and modularity of the synthesis described for deguelin and tephrosin (retrosynthetic analysis depicted) should facilitate access to labeled analogues to dissect the mechanism of action of this important pharmacophore.
Structural elucidation and chemical conversion of amorphispironone, a novel spironone from Amorpha fruticosa, to rotenoids
Terada,Kokumai,Konoshima,Kozuka,Haruna,Ito,Estes,Li,Wang,Lee
, p. 187 - 190 (2007/10/02)
To search for possible antitumor promoters, we carried out an investigation of the leaves of Amorpha fruticosa L. (Leguminosae). The novel spironone type rotenoid, amorphispironone (1), was isolated together with four known rotenoids, tephrosin (2), amorphigenin (3), 12a-hydroxyamorphigenin (4) and 12a-hydroxydalpanol (5). Some of these compounds were inhibitors of Epstein-Barr virus early antigen activation induced by 12-O-tetradecanoylphorbol-13-acetate. The structure of 1 was determined from 2D-NMR spectral data and difference NOE experiments. Amorphispironone (1) was also converted to known rotenoids in order to confirm the proposed structure.
