title: Asymmetric Total Synthesis of (-)-Englerin A through Catalytic Diastereo- and Enantioselective Carbonyl Ylide Cycloaddition.
abstract: An asymmetric total synthesis of the guaiane sesquiterpene (-)-englerin A, a potent and selective inhibitor of the growth of renal cancer cell lines, was accomplished. The basis of the approach is a highly diastereo- and enantioselective carbonyl ylide cycloaddition with an ethyl vinyl ether dipolarophile under catalysis by dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], [Rh2 (S-TCPTTL)4 ], to construct the oxabicyclo[3.2.1]octane framework with concomitant introduction of the oxygen substituent at C9 on the exo-face. Another notable feature of the synthesis is ruthenium tetraoxide-catalyzed chemoselective oxidative conversion of C9 ethyl ether to C9 acetate.
authors.affiliation: Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812 (Japan), Fax: (+81) 11-706-981.
authors.forename: Taiki
authors.initials: T
authors.lastname: Hanari
authors.affiliation: Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812 (Japan), Fax: (+81) 11-706-981.
authors.forename: Naoyuki
authors.initials: N
authors.lastname: Shimada
authors.affiliation: Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812 (Japan), Fax: (+81) 11-706-981.
authors.forename: Yasunobu
authors.initials: Y
authors.lastname: Kurosaki
authors.affiliation: Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812 (Japan), Fax: (+81) 11-706-981.
authors.forename: Neetipalli
authors.initials: N
authors.lastname: Thrimurtulu
authors.affiliation: Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812 (Japan), Fax: (+81) 11-706-981.
authors.forename: Hisanori
authors.initials: H
authors.lastname: Nambu
authors.affiliation: Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812 (Japan), Fax: (+81) 11-706-981. anada@pharm.hokudai.ac.jp.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Anada
authors.affiliation: Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812 (Japan), Fax: (+81) 11-706-981. hsmt@pharm.hokudai.ac.jp.
authors.forename: Shunichi
authors.initials: S
authors.lastname: Hashimoto
mesh_terms: D000970:Antineoplastic Agents / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D001685:Biological Factors / Q000737:chemistry; D002384:Catalysis; D045744:Cell Line, Tumor; D056831:Coordination Complexes / Q000737:chemistry*; D061565:Cycloaddition Reaction; D005019:Ethyl Ethers / Q000737:chemistry*; D006801:Humans; D007680:Kidney Neoplasms / Q000737:chemistry* / Q000473:pathology; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry; D045789:Sesquiterpenes, Guaiane / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000970:Antineoplastic Agents; D001685:Biological Factors; D056831:Coordination Complexes; D005019:Ethyl Ethers; D045789:Sesquiterpenes, Guaiane; C000606354:dirhodium(II) tetrakis(N-tetrachlorophthaloyl-(S)-tert-leucinate); C534971:englerin A; D012238:Rhodium
keywords: (−)-englerin A; 1,3-dipolar cycloaddition; asymmetric synthesis; carbonyl ylide; dirhodium(II) complexes; total synthesis