Total synthesis of Amaryllidaceae alkaloids, (+)-vittatine and (+)-haemanthamine, starting from d-glucose
2007; Elsevier BV; Volume: 63; Issue: 30 Linguagem: Inglês
10.1016/j.tet.2007.05.041
ISSN1464-5416
AutoresMasahiro Bohno, Kazuteru Sugie, Hidetoshi Imase, Yusmeeraz Yusof, Takeshi Oishi, Noritaka Chida,
Tópico(s)Advanced Synthetic Organic Chemistry
ResumoThe 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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