Total synthesis of Amaryllidaceae alkaloids, (+)-vittatine and (+)-haemanthamine, starting from d-glucose

Masahiro Bohno, Kazuteru Sugie, Hidetoshi Imase, Yusralina Binti Yusof, Takeshi Oishi, Noritaka Chida

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

The stereoselective total synthesis of (+)-vittatine 1 and (+)-haemanthamine 2 starting from d-glucose is described. The cyclohexene ring in 1 was prepared in an optically active form from d-glucose using Ferrier's carbocyclization reaction, and the critical quaternary carbon was stereoselectively generated via chirality transfer by the Claisen rearrangement of cyclohexenol 6. The hexahydroindole skeleton was effectively constructed by the intramolecular aminomercuration-demercuration of 14, followed by Chugaev reaction to provide 16. Finally, Pictet-Spengler reaction completed the first chiral synthesis of (+)-vittatine 1. On the other hand, the α-hydroxylation of the ester 5 stereoselectively proceeded to give α-hydroxy ester 19, to which was introduced an amino function to provide 4. A similar transformation of 4, as employed in the synthesis of vittatine, furnished (+)-haemanthamine 2.

Original languageEnglish
Pages (from-to)6977-6989
Number of pages13
JournalTetrahedron
Volume63
Issue number30
DOIs
Publication statusPublished - 2007 Jul 23

Fingerprint

Amaryllidaceae Alkaloids
Esters
Glucose
Hydroxylation
Skeleton
Carbon
Chirality
hemanthamine
vittatine 1

Keywords

  • Amaryllidaceae alkaloids
  • Aminomercuration
  • Chugaev reaction
  • Claisen rearrangement
  • Haemanthamine
  • Vittatine

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

Total synthesis of Amaryllidaceae alkaloids, (+)-vittatine and (+)-haemanthamine, starting from d-glucose. / Bohno, Masahiro; Sugie, Kazuteru; Imase, Hidetoshi; Yusof, Yusralina Binti; Oishi, Takeshi; Chida, Noritaka.

In: Tetrahedron, Vol. 63, No. 30, 23.07.2007, p. 6977-6989.

Research output: Contribution to journalArticle

Bohno, Masahiro ; Sugie, Kazuteru ; Imase, Hidetoshi ; Yusof, Yusralina Binti ; Oishi, Takeshi ; Chida, Noritaka. / Total synthesis of Amaryllidaceae alkaloids, (+)-vittatine and (+)-haemanthamine, starting from d-glucose. In: Tetrahedron. 2007 ; Vol. 63, No. 30. pp. 6977-6989.
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AU - Oishi, Takeshi

AU - Chida, Noritaka

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N2 - The stereoselective total synthesis of (+)-vittatine 1 and (+)-haemanthamine 2 starting from d-glucose is described. The cyclohexene ring in 1 was prepared in an optically active form from d-glucose using Ferrier's carbocyclization reaction, and the critical quaternary carbon was stereoselectively generated via chirality transfer by the Claisen rearrangement of cyclohexenol 6. The hexahydroindole skeleton was effectively constructed by the intramolecular aminomercuration-demercuration of 14, followed by Chugaev reaction to provide 16. Finally, Pictet-Spengler reaction completed the first chiral synthesis of (+)-vittatine 1. On the other hand, the α-hydroxylation of the ester 5 stereoselectively proceeded to give α-hydroxy ester 19, to which was introduced an amino function to provide 4. A similar transformation of 4, as employed in the synthesis of vittatine, furnished (+)-haemanthamine 2.

AB - The stereoselective total synthesis of (+)-vittatine 1 and (+)-haemanthamine 2 starting from d-glucose is described. The cyclohexene ring in 1 was prepared in an optically active form from d-glucose using Ferrier's carbocyclization reaction, and the critical quaternary carbon was stereoselectively generated via chirality transfer by the Claisen rearrangement of cyclohexenol 6. The hexahydroindole skeleton was effectively constructed by the intramolecular aminomercuration-demercuration of 14, followed by Chugaev reaction to provide 16. Finally, Pictet-Spengler reaction completed the first chiral synthesis of (+)-vittatine 1. On the other hand, the α-hydroxylation of the ester 5 stereoselectively proceeded to give α-hydroxy ester 19, to which was introduced an amino function to provide 4. A similar transformation of 4, as employed in the synthesis of vittatine, furnished (+)-haemanthamine 2.

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