Nickel-catalyzed intermolecular reductive couplings of alkynes and aldehydes ; Enantioselective synthesis of (-)-terpestacin and structural revision of siccanol using catalytic stereoselective fragment couplings and macrocyclizations
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004.
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| Format: | Thesis |
| Language: | eng |
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Massachusetts Institute of Technology
2005
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| Online Access: | http://hdl.handle.net/1721.1/17734 |
| _version_ | 1826214712381014016 |
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| author | Chan, Johann, 1976- |
| author2 | Timothy F. Jamison. |
| author_facet | Timothy F. Jamison. Chan, Johann, 1976- |
| author_sort | Chan, Johann, 1976- |
| collection | MIT |
| description | Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004. |
| first_indexed | 2024-09-23T16:10:18Z |
| format | Thesis |
| id | mit-1721.1/17734 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T16:10:18Z |
| publishDate | 2005 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/177342019-04-12T14:02:25Z Nickel-catalyzed intermolecular reductive couplings of alkynes and aldehydes ; Enantioselective synthesis of (-)-terpestacin and structural revision of siccanol using catalytic stereoselective fragment couplings and macrocyclizations Nickel-catalyzed intermolecular reductive couplings of alkynes and aldehydes Chan, Johann, 1976- 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, 2004. Vita. Includes bibliographical references. I. Nickel-Catalyzed Intermolecular Reductive Coupling of Alkynes and Aldehydes. Alkynes and aldehydes were coupled reductively in a single catalytic reaction to yield di- and trisubstituted allylic alcohols with high stereoselectivity and regioselectivity. In most cases, a 1:1 ratio of alkyne to aldehyde was sufficient for efficient coupling. The yield and regioselectivity were strongly dependent on the phosphine ligand, but the allylic alcohols formed were invariably the products of cis addition to the alkyne. [Image] ... II. Enantioselective Synthesis of (-)-Terpestacin and Structural Revision of Siccanol Using Catalytic Stereoselective Fragment Couplings and Macrocyclizations. (-)-Terpestacin (1), (naturally occurring enantiomer) and (+)-1 -epi-terpestacin (2) were prepared using catalyst-controlled, stereoselective intermolecular reductive couplings of alkyne 9 and aldehyde 10. Related to enantioselective methods developed in our laboratory, these stereoselective fragment couplings were instrumental in confirming that "siccanol" is not 11-epi-terpestacin, but in fact is (-)-terpestacin itself. by Johann Chan. Ph.D. 2005-06-02T18:26:27Z 2005-06-02T18:26:27Z 2004 2004 Thesis http://hdl.handle.net/1721.1/17734 56474296 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 217 leaves 4936566 bytes 4936372 bytes application/pdf application/pdf application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry. Chan, Johann, 1976- Nickel-catalyzed intermolecular reductive couplings of alkynes and aldehydes ; Enantioselective synthesis of (-)-terpestacin and structural revision of siccanol using catalytic stereoselective fragment couplings and macrocyclizations |
| title | Nickel-catalyzed intermolecular reductive couplings of alkynes and aldehydes ; Enantioselective synthesis of (-)-terpestacin and structural revision of siccanol using catalytic stereoselective fragment couplings and macrocyclizations |
| title_full | Nickel-catalyzed intermolecular reductive couplings of alkynes and aldehydes ; Enantioselective synthesis of (-)-terpestacin and structural revision of siccanol using catalytic stereoselective fragment couplings and macrocyclizations |
| title_fullStr | Nickel-catalyzed intermolecular reductive couplings of alkynes and aldehydes ; Enantioselective synthesis of (-)-terpestacin and structural revision of siccanol using catalytic stereoselective fragment couplings and macrocyclizations |
| title_full_unstemmed | Nickel-catalyzed intermolecular reductive couplings of alkynes and aldehydes ; Enantioselective synthesis of (-)-terpestacin and structural revision of siccanol using catalytic stereoselective fragment couplings and macrocyclizations |
| title_short | Nickel-catalyzed intermolecular reductive couplings of alkynes and aldehydes ; Enantioselective synthesis of (-)-terpestacin and structural revision of siccanol using catalytic stereoselective fragment couplings and macrocyclizations |
| title_sort | nickel catalyzed intermolecular reductive couplings of alkynes and aldehydes enantioselective synthesis of terpestacin and structural revision of siccanol using catalytic stereoselective fragment couplings and macrocyclizations |
| topic | Chemistry. |
| url | http://hdl.handle.net/1721.1/17734 |
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