The reactivity of epoxides with lithium 2,2,6,6-tetramethylpiperidide in combination with organolithiums or grignard reagents.
The scope and limitations of lithium 2,2,6,6-tetramethylpiperidide (LTMP)-modified reductive alkylation of epoxides is detailed. A variety of organolithiums are added to terminal and 2,2-disubstituted epoxides in the presence of LTMP to generate alkenes in a completely regio- and highly stereoselect...
| Main Authors: | , , |
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| Format: | Journal article |
| Language: | English |
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2007
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| _version_ | 1797080785329586176 |
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| author | Hodgson, D Fleming, M Stanway, S |
| author_facet | Hodgson, D Fleming, M Stanway, S |
| author_sort | Hodgson, D |
| collection | OXFORD |
| description | The scope and limitations of lithium 2,2,6,6-tetramethylpiperidide (LTMP)-modified reductive alkylation of epoxides is detailed. A variety of organolithiums are added to terminal and 2,2-disubstituted epoxides in the presence of LTMP to generate alkenes in a completely regio- and highly stereoselective manner. Arylated alkenes, dienes, allylsilanes, and enynes are accessed using this procedure. The methodology is applied in the synthesis of the roller leaf moth pheromone, (3E,5Z)-dodecadienyl acetate. The corresponding reaction without LTMP has also been examined, and a study using deuterated epoxides provides insight into the mechanism. In the presence of LTMP, Grignard reagents are also shown to produce E-alkenes directly from epoxides. |
| first_indexed | 2024-03-07T01:05:09Z |
| format | Journal article |
| id | oxford-uuid:8b157a9f-440e-4119-9fc3-88afb8b457de |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T01:05:09Z |
| publishDate | 2007 |
| record_format | dspace |
| spelling | oxford-uuid:8b157a9f-440e-4119-9fc3-88afb8b457de2022-03-26T22:35:48ZThe reactivity of epoxides with lithium 2,2,6,6-tetramethylpiperidide in combination with organolithiums or grignard reagents.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:8b157a9f-440e-4119-9fc3-88afb8b457deEnglishSymplectic Elements at Oxford2007Hodgson, DFleming, MStanway, SThe scope and limitations of lithium 2,2,6,6-tetramethylpiperidide (LTMP)-modified reductive alkylation of epoxides is detailed. A variety of organolithiums are added to terminal and 2,2-disubstituted epoxides in the presence of LTMP to generate alkenes in a completely regio- and highly stereoselective manner. Arylated alkenes, dienes, allylsilanes, and enynes are accessed using this procedure. The methodology is applied in the synthesis of the roller leaf moth pheromone, (3E,5Z)-dodecadienyl acetate. The corresponding reaction without LTMP has also been examined, and a study using deuterated epoxides provides insight into the mechanism. In the presence of LTMP, Grignard reagents are also shown to produce E-alkenes directly from epoxides. |
| spellingShingle | Hodgson, D Fleming, M Stanway, S The reactivity of epoxides with lithium 2,2,6,6-tetramethylpiperidide in combination with organolithiums or grignard reagents. |
| title | The reactivity of epoxides with lithium 2,2,6,6-tetramethylpiperidide in combination with organolithiums or grignard reagents. |
| title_full | The reactivity of epoxides with lithium 2,2,6,6-tetramethylpiperidide in combination with organolithiums or grignard reagents. |
| title_fullStr | The reactivity of epoxides with lithium 2,2,6,6-tetramethylpiperidide in combination with organolithiums or grignard reagents. |
| title_full_unstemmed | The reactivity of epoxides with lithium 2,2,6,6-tetramethylpiperidide in combination with organolithiums or grignard reagents. |
| title_short | The reactivity of epoxides with lithium 2,2,6,6-tetramethylpiperidide in combination with organolithiums or grignard reagents. |
| title_sort | reactivity of epoxides with lithium 2 2 6 6 tetramethylpiperidide in combination with organolithiums or grignard reagents |
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