Vinyloxiranes 6a-b and vinylaziridines 7a-b were prepared efficiently from halocyclohexadiene-cis-diols 1. Reactions of 6 and 7 with a variety of organometallic reagents were investigated in order to determine the stereo- and regiochemistry of ring opening with carbon nucleophiles. The results indicate that 6 and 7 could serve as useful new synthons for C-disaccharides and Amaryllidaceae alkaloid syntheses.
The utility of synthon 7b has been demonstrated by a concise enantiocontrolled synthesis of (+)-pancratistatin (9). The key step involved the S<sub>N</sub>2 opening of 7b with the aryl cyanocuprate derived from amide 217 to generate the pivotal cyclization precursor. / Ph. D.
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/38237 |
| Date | 06 June 2008 |
| Creators | Tian, Xinrong |
| Contributors | Chemistry, Hudlicky, Tomas, Gibson, Harry W., Hanson, Brian E., Tanko, James M., White, Robert H. |
| Publisher | Virginia Tech |
| Source Sets | Virginia Tech Theses and Dissertation |
| Language | English |
| Detected Language | English |
| Type | Dissertation, Text |
| Format | x, 156 leaves, BTD, application/pdf, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
| Relation | OCLC# 33191068, LD5655.V856_1995.T536.pdf |
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