Nickel-catalyzed reductive coupling reactions of 1,6-enynes and the total synthesis of (+)-acutiphycin
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007.
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| Format: | Thesis |
| Language: | eng |
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Massachusetts Institute of Technology
2007
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| Online Access: | http://hdl.handle.net/1721.1/38622 |
| _version_ | 1811088774330843136 |
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| author | Moslin, Ryan Thomas McLeod |
| author2 | Timothy F. Jamison. |
| author_facet | Timothy F. Jamison. Moslin, Ryan Thomas McLeod |
| author_sort | Moslin, Ryan Thomas McLeod |
| collection | MIT |
| description | Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007. |
| first_indexed | 2024-09-23T14:07:00Z |
| format | Thesis |
| id | mit-1721.1/38622 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T14:07:00Z |
| publishDate | 2007 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/386222019-04-10T12:12:50Z Nickel-catalyzed reductive coupling reactions of 1,6-enynes and the total synthesis of (+)-acutiphycin Moslin, Ryan Thomas McLeod Timothy F. Jamison. Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Dept. of Chemistry. Chemistry. Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007. Vita. Includes bibliographical references. Nickel-Catalyzed Reductive Coupling Reactions of Aldehydes and Chiral 1,6-Enynes. A study of nickel-catalyzed reductive coupling reactions of aldehydes and chiral 1,6-enynes has provided evidence for stereospecific ligand substitution from a planar three-coordinate nickel species as a plausible explanation of regioselectivity in the nickel-catalyzed reductive coupling of aldehydes and 1,6-enynes. In the absence of a phosphine additive, high regioselectivity and high diastereoselectivity are obtained as a direct result of coordination of both the alkyne and the olefin to the metal center during the C-C bond-forming step. ... Total Synthesis of (+)-Acutiphycin. Synthetic studies toward the total synthesis of (+)-acutiphycin led to, and were in turn further developed by, the study of nickel-catalyzed reductive coupling reactions of 1,6-enynes and aldehydes. ... Ultimately, though not employing the nickel-catalyzed reaction, a highly convergent total synthesis of (+)-acutiphycin featuring an intermolecular SmI2-mediated Reformatsky coupling reaction and macrolactonization initiated by a retro-ene reaction of an alkoxyalkyne was developed. The resulting synthesis was 18 steps in the longest linear sequence from either methyl acetoacetate or isobutyraldehyde. ... by Ryan Thomas McLeod Moslin. Ph.D. 2007-08-29T20:36:28Z 2007-08-29T20:36:28Z 2007 2007 Thesis http://hdl.handle.net/1721.1/38622 156995693 eng M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 200 p. application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry. Moslin, Ryan Thomas McLeod Nickel-catalyzed reductive coupling reactions of 1,6-enynes and the total synthesis of (+)-acutiphycin |
| title | Nickel-catalyzed reductive coupling reactions of 1,6-enynes and the total synthesis of (+)-acutiphycin |
| title_full | Nickel-catalyzed reductive coupling reactions of 1,6-enynes and the total synthesis of (+)-acutiphycin |
| title_fullStr | Nickel-catalyzed reductive coupling reactions of 1,6-enynes and the total synthesis of (+)-acutiphycin |
| title_full_unstemmed | Nickel-catalyzed reductive coupling reactions of 1,6-enynes and the total synthesis of (+)-acutiphycin |
| title_short | Nickel-catalyzed reductive coupling reactions of 1,6-enynes and the total synthesis of (+)-acutiphycin |
| title_sort | nickel catalyzed reductive coupling reactions of 1 6 enynes and the total synthesis of acutiphycin |
| topic | Chemistry. |
| url | http://hdl.handle.net/1721.1/38622 |
| work_keys_str_mv | AT moslinryanthomasmcleod nickelcatalyzedreductivecouplingreactionsof16enynesandthetotalsynthesisofacutiphycin |