51371-13-2Relevant academic research and scientific papers
Total synthesis, structural revision and biological evaluation of γ-elemene-type sesquiterpenes
Yuan, Changchun,Zhong, Shangyong,Li, Xingyi,Wang, Yanhong,Xun, Miao-Miao,Bai, Yunli,Zhu, Kongkai
, p. 7843 - 7850 (2018)
Total synthesis and absolute configuration confirmation of γ-elemene-type sesquiterpenes, which possess vast potential for biological activities, was investigated based on a convergent synthetic strategy. A key intermediate with all functional groups of this family of natural products was accessed by an intermolecular aldol reaction and then an acetylation of a known ketone (12) derived from commercially available verbenone. The versatile intermediate can be easily transformed into structurally different γ-elemene-type sesquiterpenes based on control of base-promoted cyclization manipulation in different solvents. The utility of this robust approach is illustrated by the first syntheses of elema-1,3,7(11),8-tetraen-8,12-lactam (4′) and 8β-methoxy-isogermafurenolide (6a), as well as the syntheses of elem-1,3,7,8-tetraen-8,12-olide (3) and hydroxyisogermafurenolide (5) in only 6 or 7 steps. In addition, the structure of the reported 5βH-elem-1,3,7,8-tetraen-8,12-olide (1) was revised as elem-1,3,7,8-tetraen-8,12-olide (3) by comparison of their identified datum, and the absolute configuration of elema-1,3,7(11),8-tetraen-8,12-lactam was confirmed as 4′. Furthermore, the inhibitory effect of all synthesized natural compounds and their natural analogues on cancer cell proliferation was evaluated. Among them compounds 3, 4 and 4′ were found to possess potent inhibitory activity against Kasumi-1 and Pfeiffer. Meanwhile, preliminary structure-activity relationships for these compounds are discussed.
Efficient synthesis of the anticancer β-elemene and other bioactive elemanes from sustainable germacrone
Barrero, Alejandro F.,Herrador, M. Mar,Quilez Del Moral, Jose F.,Arteaga, Pilar,Meine, Niklas,Perez-Morales, M. Carmen,Catalan, Julieta V.
experimental part, p. 1118 - 1125 (2011/04/15)
Highly efficient preparations of anticancer β-elemene and other bioactive elemanes were carried out using the natural product germacrone as a renewable starting material. The syntheses were achieved in only 3-5 steps with excellent overall yields (43-54%). An enantioselective approach to these molecules is also described
Carbocyclic Construction by the Sigmatropic Rearrangement of Cyclic Sulfonium Ylides. A New Entry for the Stereoselective Synthesis of Substituted Cyclohexanones
Kido, Fusao,Yamaji, Kazuo,Sinha, Subhash C.,Abiko, Toshiya,Kato, Michiharu
, p. 7697 - 7714 (2007/10/02)
The rhodium(II)-catalyzed cyclization of acyclic α-diazo-β-keto esters 1c,d provided stereoselectively the highly substituted cyclohexanones 3c,d respectively, by the sigmatropic rearrangement via stereocontrolled nine-membered allylsulfonium ylides 2c,d.Further elaboration of 3d toward the cyclohexanone 36 accomplished asymmetric formal syntheses of the representative elemanoids, 37 and 38.The compound 3c was transformed into the cyclohexanone 34a and cyclohexene 43, which could serve as the key intermediates for the synthesis of natural products possessing contigously cis-arranged trimethylcyclohexanone and its related moieties, respectively.
The Use of 4,4-Disubstituted Nopinones for Natural-Product Synthesis. Synthesis of Elemanoid Sesquiterpenes
Kato, Michiharu,Watanabe, Masataka,Vogler, Bernhard,Awen, Bahlul Z.,Masuda, Yoshiaki,et al.
, p. 7071 - 7076 (2007/10/02)
A general and convenient synthetic route to 4,4-disubstituted nopinones 14 from (+)-nopinone (1) is developed and applied to the asymmetric synthesis of some representative elemanoid sesquiterpenes.Phenylsulfenylation of 1 provided sulfide 6 in high yields.A convenient transformation of 6 to 3-(phenylsulfonyl)-4,4-disubstituted-nopinones 13 was accomplished by (i) m-CPBA oxidation of a sulfide compound followed by the Pummerer rearrangement and (ii) the conjugate addition of carbon nucleophiles to the resulting enones, 6 -> 8 -> 9 and 9 -> 10, 11 -> 13.Subsequent reductive desulfurization of the adducts 13 provided 14 in good overall yield from 1.Bicyclic ketones 14 are envisioned as promising intermediates for natural product synthesis.As examples, syntheses of two elemanoid sesquiterpenes, β-elemenone (16) and eleman-8β,12-olide (17) in optically active form from (1R,4S,5S)-4,6,6-trimethyl-4-vinylbicycloheptan-2-one (14a) were carried out.
A Key Intermediate for the Chiral Synthesis of Elemanoids. Synthesis of (+)-β-Elemenone
Kato, Michiharu,Vogler, Bernhard,Tooyama, Youichi,Yoshikoshi,Akira
, p. 151 - 154 (2007/10/02)
(1R,5S)-3-Phenylsulfenyl-6,6-dimethylbicycloheptanone obtained from (+)-nopinone was transformed into (1R,4S,5S)-4-methyl-4-vinylbicycloheptan-2-one, whose cyclobutane ring was cleaved with BF3*EtO2-Zn(OAc)2 in acetic anhydride to provide (4S,5S)-1-acetoxy-4-isopropenyl-5-methyl-5-vinyl-1-cyclohexene (5), the key intermediate, in a highly regio- and stereoselective manner.Regioselective introduction of a three-carbon unit to 5 with acetone followed by dehydration yielded (+)-β-elemenone.
TOTAL SYNTHESIS OF VARIOUS ELEMANOLIDES
Friedrich, Dirk,Bohlmann, Ferdinand
, p. 1369 - 1392 (2007/10/02)
Starting with a suitable substituted divinyl cyclohexanone, eleven naturally occurring 12.8-elemanolides bearing exo-methylene or methyl groups at C-11 and differing in substitution as well as in relative configuration, have been synthesized in racemic form.An approach to elemanolides with additional oxygen functionalities is principally possible by modification of the basic concept.Methods for the oxidative generation of terpenoid exo-methylene lactone and furan units are exemplified by synthesis of menthofuran and the p-menthenolides from isopulegols.
STEREOSELECTIVE TOTAL SYNTHESIS OF (4S)-trans-β-ELEMENONE FROM (S)-2-CYCLOHEXEN-1-OL
Sato, Toshio,Gotoh, Yoshihiko,Watanabe, Makoto,Fujisawa, Tamotsu
, p. 1533 - 1536 (2007/10/02)
Stereoselective first total synthesis of (4S)-trans-β-elemenone was achieved from (S)-2-cyclohexen-1-ol, prepared easily by the asymmetric reduction of 2-cyclohexen-1-one with chiral hydride reagent.
A NEW FORMAL TOTAL SYNTHESIS OF β-ELEMENONE
Soria, O.,Maldonado, L. A.
, p. 1093 - 1097 (2007/10/02)
A short, stereoselective synthesis of an intermediate in Grieco's synthesis of β-elemenone is described
