70878-71-6Relevant 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.
Total synthesis of s (+)-curcuphenol, s (+)-curcuquinone and s (+)-curcuhydroquinone
Chinta, Ramakoteswara Rao,Harikrishna,Tulam, Vijaya Kumar,Bejjanki, Naveen Kumar,Mainkar, Prathama S.,Dubey
, p. 771 - 778 (2016/03/01)
A synthesis of (-)-curcuphenol, (-)-curcuquinone and (-)-curcuhydroquinone from o-valerolactone is described. The key steps include an Evans asymmetric methylation of 5-(benzyloxy)pentanoic acid (5), an oxidative aromatization of enone (11) and a regioselective oxidation of the phenol to o-quinone derivative with bis(trifluoro acetate)iodobenzene.
Total Synthesis of (-)-Bacchopetiolone via an Asymmetric Hydroxylative Phenol Dearomatization/[4+2]-Dimerization Cascade Promoted by a Novel Salen-Type Chiral Iodane
Coffinier, Romain,Assal, Mourad El,Peixoto, Philippe A.,Bosset, Cyril,Miqueu, Karinne,Sotiropoulos, Jean-Marc,Pouységu, Laurent,Quideau, Stéphane
, p. 1120 - 1123 (2016/03/15)
The first total and biomimetic synthesis of the natural bis(sesquiterpene) (-)-bacchopetiolone (revised structure) was completed through a highly diastereoselective hydroxylative phenol dearomatization/[4+2]-dimerization cascade conversion of (+)-curcuphe
Preparation and use of enantioenriched 2-aryl-propylsulfonylbenzene derivatives as valuable building blocks for the enantioselective synthesis of bisabolane sesquiterpenes
Serra, Stefano
, p. 1561 - 1572 (2015/02/05)
We have demonstrated that different enantioenriched 2-arylpropylsufonylbenzene derivatives are very useful building blocks for the synthesis of aromatic bisabolane sesquiterpenes. Their preparation and the exploitation of their chemical reactivity have been comprehensively investigated. Accordingly, the naturally occurring bisabolane sesquiterpenes (-)-curcuphenol, (-)-xanthorrhizol, (+)-glandulone A, (+)-curcudiol, (+)-turmerone and (+)-curcudiol-10-one were synthesized in high enantiomeric purity. It is worth noting that the compounds (+)-curcudiol-10-one and (+)-glandulone A were prepared in enantioenriched form for the first time. Through the proposed synthetic approaches, we were able to confirm both chemical structures and the absolute configurations previously assigned to the two aforementioned sesquiterpenes.
Expedient synthesis of (R)-curcuphenol: A chiral pool strategy
Feng, Jing,Zhu, Guili,Liu, Bo,Zhou, Xiangdong
, p. 23 - 26 (2013/08/24)
Curcuphenol is an interesting sesquiterpenoid with diverse bioactivities. Exploration of a concise and scalable synthetic route is still of significance in spite that many asymmetric total syntheses have been achieved. We report an expedient asymmetric synthesis of (R)-curcuphenol from citronellal, which features only two purification operations in the overall six-step synthesis. Curcuphenol is an interesting terpenoid with diverse bioactivities. We report an expedient asymmetric synthesis of curcuphenol from citronellal which features only two purification operations in the overall six-step synthesis. Copyright
Application of the lithiation-borylation reaction to the rapid and enantioselective synthesis of the bisabolane family of sesquiterpenes
Aggarwal, Varinder K.,Ball, Liam T.,Carobene, Simon,Connelly, Rickki L.,Hesse, Matthew J.,Partridge, Benjamin M.,Roth, Philippe,Thomas, Stephen P.,Webster, Matthew P.
, p. 9230 - 9232 (2012/09/10)
The expedient enantioselective synthesis of 5 bisabolane sesquiterpenes has been achieved using a common, one-pot lithiation-borylation reaction of secondary benzylic carbamates and either protodeboronation or oxidation to give the natural products in few
Efficient enantioselective total synthesis of (+)-helianane
Soga, Kana,Kanematsu, Makoto,Yoshida, Masahiro,Shishido, Kozo
scheme or table, p. 1171 - 1173 (2011/07/09)
The enantiocontrolled total synthesis of (+)-helianane, a marine-derived heterocyclic sesquiterpene, has been accomplished with an efficient chirality transfer during the Me3Al-mediated aromatic Claisen rearrangement and a ring-closing metathesis as the key steps. The absolute structure of the natural product has been firmly established by total synthesis. Georg Thieme Verlag Stuttgart - New York.
An oxidative dearomatization-induced [5 + 2] cascade enabling the syntheses of α-cedrene, α-pipitzol, and sec -cedrenol
Green, Jason C.,Pettus, Thomas R. R.
supporting information; experimental part, p. 1603 - 1608 (2011/04/16)
Efficient syntheses of α-cedrene (1), α-pipitzol (2), and sec-cedrenol (3) were carried out using a new method, which was inspired by the proposed biosynthesis of the tricyclic skeleton of cedrol (12). The key transformation begins with the oxidative dearomatization of curcuphenol (5a) followed by an intramolecular [5 + 2] cycloaddition of the respective phenoxonium intermediate across the tethered olefin. The benzylic stereocenter effectively guides the formation of the first two stereocenters during the [5 + 2] reaction. The cascade then terminates with the selective incorporation of acetic acid to generate a third stereocenter, setting it apart from other previous cationic [5 + 2] reactions. The phenolic precursors (5a-h) are constructed from readily available salicylaldehydes, either as the racemate (one pot) or as a specific enantiomer (four pots) by a modification to our method for the generation of ortho-quinone methides (o-QMs).
Total synthesis and repudiation of the helianane family
Green, Jason C.,Jimenez-Alonso, Sandra,Brown, Eric. R.,Pettus, Thomas R. R.
supporting information; experimental part, p. 5500 - 5503 (2011/12/22)
Total syntheses of two structures purported as (+)-heliananes were completed in six pots. Spectral comparisons, between the synthetic and natural compounds, revealed a misassignment of the eight-membered ring in the heliananes. The key step in the synthes
Enantioselective synthesis of (R)- and (S)-curcumene and curcuphenol: an efficient chemoenzymatic route
Kamal, Ahmed,Malik, M. Shaheer,Shaik, Ahmad Ali,Azeeza, Shaik
, p. 2547 - 2553 (2008/03/15)
An efficient enantioselective synthesis of curcumene and curcuphenol is described. The key intermediates, substituted butanoates 7a and 7b and their acids 8a and 8b are obtained in high enantiopurity (>99% ee) by a lipase-catalyzed kinetic resolution proc
