| [PMID]: | 22924746 |
| [Au] Autor: | Zhang XM; Shao H; Tu YQ; Zhang FM; Wang SH |
| [Ad] Endereço: | State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000, PR China. |
| [Ti] Título: | Total syntheses of (+)-alopecuridine, (+)-sieboldine A, and (-)-lycojapodine A. |
| [So] Source: | J Org Chem;77(18):8174-81, 2012 Sep 21. |
| [Is] ISSN: | 1520-6904 |
| [Cp] País de publicação: | United States |
| [La] Idioma: | eng |
| [Ab] Resumo: | (+)-Alopecuridine, (+)-sieboldine A, and (-)-lycojapodine A, three structurally unique and related lycopodium alkaloids, have been synthesized in enantiomeric forms through an efficient strategy. The main synthetic approach for (+)-alopecuridine features a semipinacol rearrangement of hydroxyl epoxide to construct the spiro 6,9-azacarbocycles with an all-carbon quaternary center and a late-stage SmI(2)-mediated intramolecular coupling to form the 5-membered ring. Subsequently, the biomimetic synthesis of (+)-sieboldine A and (-)-lycojapodine A was accomplished successfully through two different bioinspired oxidations after a wide search for the oxidation methods. As a result, (+)-sieboldine A was derived from (+)-alopecuridine through an N-oxidation/nitrone formation process and (-)-lycojapodine A through an interesting cyclic hemiketal formation/oxidative diol cleavage pathway. These results confirmed the biogenetic relationship among the three alkaloids. |
| [Mh] Termos MeSH primário: |
Alcaloides/química Alcaloides/síntese química Compostos de Epóxi/química Compostos Heterocíclicos de 4 ou mais Anéis/química Compostos Heterocíclicos de 4 ou mais Anéis/síntese química Óxidos de Nitrogênio/química Compostos de Espiro/química
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| [Mh] Termos MeSH secundário: |
Estrutura Molecular Oxirredução Estereoisomerismo
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| [Pt] Tipo de publicação: | JOURNAL ARTICLE; RESEARCH SUPPORT, NON-U.S. GOV'T |
[Nm] Nome de substância:
| 0 (Alkaloids); 0 (Epoxy Compounds); 0 (Heterocyclic Compounds with 4 or More Rings); 0 (Nitrogen Oxides); 0 (Spiro Compounds); 0 (alopecuridine); 0 (lycojapodine A); 0 (nitrones); 0 (sieboldine A) |
| [Em] Mês de entrada: | 1304 |
| [Sb] Subgrupo de revista: | IM |
| [Da] Data de entrada para processamento: | 120921 |
| [St] Status: | MEDLINE |
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