72441-70-4Relevant academic research and scientific papers
Highly Stereocontrolled Total Syntheses of Cedrane Sesquiterpenes via Cascade [5+2] Cycloaddition/Etherification
Chi, Zhiyong,Li, Xiangxin,Xie, Zhixiang,Zhang, Yuhan
supporting information, p. 183 - 189 (2021/12/21)
Cedrane sesquiterpenes possess common tricyclo[5.3.1.01,5]undecane core structure. The varied oxa-five-membered ring decorating their core structure to form 8-oxa-tetracyclo[7.2.2.01,5.06,13]tridecane framework, containing six consecutive chiral centers (including two all-carbon quaternary centers and one oxygenated quaternary carbon center), has proven to be a synthetic challenge and a biosynthetic mystery to date. Herein, we reported a distinct and biomimetic strategy to these sesquiterpenes resulting in the concise asymmetric total syntheses of three cedrane sesquiterpenes from simple commercially available building blocks. Key feature is exploitation of a cascade oxidative dearomatization-induced [5+2] cycloaddition/etherification to highly stereocontrolled construct 8-oxa-tetracyclo[7.2.2.01,5.06,13]tridecane framework with five contiguous chiral centers in one step. In addition, a metal-free I2-catalyzed and DMSO-mediated oxidative dehydroaromatization was applied to prepare curcuphenol and its derivatives from the highly functionalized cyclohexenones with minimal manipulations.
Absolute Configurations of Stink Bug- And Plant-Produced Sesquipiperitols via Synthesis of All Stereoisomers
Khrimian, Ashot,Guggilapu, Sravanthi D.,Guzman, Filadelfo,Blassioli-Moraes, Maria Carolina,Borges, Miguel
, p. 2281 - 2286 (2020/07/30)
Sesquipiperitol is a sesquiterpene alcohol, some stereoisomers of which were found in several plant species. The biological role of these compounds in plants and their absolute configurations have not been reported. Recently, we found that 1S,6S,7R stereoisomer of sesquipiperitol was a key precursor in the biosynthesis of the harlequin bug, Murgantia histrionica, pheromone, which consists of two stereoisomeric zingiberenol oxides. In addition, the Tibraca limbativentris stink bug was shown to produce two sesquipiperitol stereoisomers as minor components in their male-produced sex pheromone, the main constituents of which were zingiberenols. To determine absolute configurations of plant- and stink-bug-produced sesquipiperitols, we undertook syntheses of all stereoisomers of this sesquiterpene alcohol. The syntheses were based on 1,10-bisaboladien-3-ols (aka zingiberenols) with known configurations at C-6 and C-7, the oxidation of which provided sesquipiperitone precursors with retention of configurations of these stereogenic centers. The foremost challenge of the synthetic endeavor was the assignment of absolute configurations of secondary carbinol centers, which was resolved by NMR analyses of corresponding Mosher's esters. Thus, the availability of all eight diastereomers allowed us to assign sesquipiperitols from Fitzroya cupressoides and Argyranthemum adauctum spp. jacobaeifolium plants 1S,6S,7R (16) and 1R,6R,7S (14) configurations, respectively. A chiral-phase gas-chromatographic method was developed to determine 1S,6S,7R and 1R,6S,7R (15) configurations of T. limbativentris sesquipiperitol pheromone components.
Total synthesis of bisabolane sesquiterpenoids, α-bisabol-1-one, curcumene, curcuphenol and elvirol: Utility of catalytic enamine reaction in cyclohexenone synthesis
Hagiwara, Hisahiro,Okabe, Tomoyuki,Ono, Hiroki,Kamat, Vijayendra P.,Hoshi, Takashi,Suzuki, Toshio,Ando, Masayoshi
, p. 895 - 900 (2007/10/03)
Total syntheses of α-bisabol-1-one, curcumene, curcuphenol and elvirol have been accomplished via 1,4-conjugate addition of intact aldehydes to vinyl ketones followed by an intramolecular aldol condensation.
