Explorations in organic chemistry leading to the total synthesis of (±)-gelsemine Journal Article
| Authors: | Ng, F. W.; Lin, H.; Danishefsky, S. J. |
| Article Title: | Explorations in organic chemistry leading to the total synthesis of (±)-gelsemine |
| Abstract: | The total synthesis of (±)-gelsemine (1) is described. A defining phase of the effort involved recourse to a strategic oxetane ring (see compound 25). It was constructed anticipating an intramolecular displacement of the carbon (C17)-oxygen (O4) bond (see product 48). A key intermediate in the stereospecific elaboration of the oxetane linkage was enone 22, which was susceptible to two β-face attacks leading to 24 and, thence, 25. Three sigmatropic rearrangements were employed in building the bridgehead (C20) and the spiroanilide (C7) quaternary centers en route to gelsemine. |
| Keywords: | unclassified drug; oxygen; chemical structure; alkaloids; stereospecificity; synthesis; synthesis (chemical); stereochemistry; stereoisomerism; chemical bond; anilide; carbon; chemical binding; alkaloid; chemical bonds; gelsemine; article; quaternary centers; oxetane derivative |
| Journal Title: | Journal of the American Chemical Society |
| Volume: | 124 |
| Issue: | 33 |
| ISSN: | 0002-7863 |
| Publisher: | American Chemical Society |
| Date Published: | 2002-08-21 |
| Start Page: | 9812 |
| End Page: | 9824 |
| Language: | English |
| DOI: | 10.1021/ja0204675 |
| PUBMED: | 12175241 |
| PROVIDER: | scopus |
| DOI/URL: | |
| Notes: | Addition/Correction issued, see DOI: 10.1021/ja0334558 -- Export Date: 14 November 2014 -- Source: Scopus |
