Asymmetric syntheses of diarylheptanoid natural products (−)-centrolobine and (−)-de- O-methylcentrolobine via hetero-Diels–Alder reaction catalyzed by dirhodium(II) tetrakis[( R)-3-(benzene-fused-phthalimido)-2-piperidinonate]

• Published in: Tetrahedron Vol. 63; no. 48; pp. 12037 - 12046
• Main Authors: Washio, Takuya, Yamaguchi, Reika, Abe, Takumi, Nambu, Hisanori, Anada, Masahiro, Hashimoto, Shunichi
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 26.11.2007; Elsevier
• Subjects: (−)-Centrolobine; (−)-De- O-methylcentrolobine; Chemistry; Chemistry, Organic; Chiral Rh(II) catalyst; Diarylheptanoids; Hetero-Diels–Alder reaction; Physical Sciences; Science & Technology; Hetero-Diels–Alder reaction; Chiral Rh(II) catalyst; (−)-De- O-methylcentrolobine; Diarylheptanoids; (−)-Centrolobine; diarylheptanoids; chiral Rh(II) catalyst; CARBONYL-COMPOUNDS; DIOSPONGIN-A; (-)-de-O-methylcentrolobine; ANTIPROLIFERATIVE DIARYLHEPTANOIDS; (-)-centrolobine; BIOLOGICAL EVALUATION; BLEPHAROCALYXINS C-E; STEREOSELECTIVE-SYNTHESIS; PRINS CYCLIZATIONS; ENANTIOSELECTIVE TOTAL-SYNTHESIS; ALPINIA-BLEPHAROCALYX; EPICALYXIN-F; hetero-Diels-Alder reaction
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2007.09.003

Catalytic asymmetric syntheses of (−)-centrolobine and (−)-de- O-methylcentrolobine have been achieved, incorporating a hetero-Diels–Alder (HDA) reaction between 4-aryl-2-silyloxy-1,3-butadienes and phenylpropargyl aldehyde derivatives as a key step. The HDA reaction using dirhodium(II) tetrakis[( R)-3-(benzene-fused-phthalimido)-2-piperidinonate], Rh 2( R-BPTPI) 4, as a chiral Lewis acid catalyst provides exclusively cis-2,6-disubstituted tetrahydropyran-4-ones in up to 93% ee. [Display omitted]