Squarate desymmetrisation–ozonolysis as an approach to β-substituted-α-ketosuccinates and squalestatin synthesis
Silylated tertiary alcohols from 1,2-addition of alkyllithiums to dialkyl squarates undergo alkene ozonolysis to give β-substituted-α-keto-β-(silyloxy)succinates. With 3-(triethylsilyloxy)butyllithium the methodology was applied to the 2,8-dioxabicyclo[3.2.1]octane core of the squalestatins. Enantio...
| Main Authors: | , , , |
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| Format: | Journal article |
| Language: | English |
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Elsevier
2019
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| _version_ | 1826299778080702464 |
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| author | Sintim, H Valade, A Harling, D Hodgson, D |
| author_facet | Sintim, H Valade, A Harling, D Hodgson, D |
| author_sort | Sintim, H |
| collection | OXFORD |
| description | Silylated tertiary alcohols from 1,2-addition of alkyllithiums to dialkyl squarates undergo alkene ozonolysis to give β-substituted-α-keto-β-(silyloxy)succinates. With 3-(triethylsilyloxy)butyllithium the methodology was applied to the 2,8-dioxabicyclo[3.2.1]octane core of the squalestatins. Enantioselective 1,2-addition to di-tert-butyl squarate using butyllithium or diethylzinc/Ti(iPrO)4 in the presence of chiral ligands (such as bisoxazolines or camphorsulfonamides, respectively) gave the corresponding tertiary alcohols in up to 67.5:32.5 er. |
| first_indexed | 2024-03-07T05:07:07Z |
| format | Journal article |
| id | oxford-uuid:da4d3ee3-b2f4-43b1-bb4b-864108faaf13 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T05:07:07Z |
| publishDate | 2019 |
| publisher | Elsevier |
| record_format | dspace |
| spelling | oxford-uuid:da4d3ee3-b2f4-43b1-bb4b-864108faaf132022-03-27T09:02:26ZSquarate desymmetrisation–ozonolysis as an approach to β-substituted-α-ketosuccinates and squalestatin synthesisJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:da4d3ee3-b2f4-43b1-bb4b-864108faaf13EnglishSymplectic Elements at OxfordElsevier2019Sintim, HValade, AHarling, DHodgson, DSilylated tertiary alcohols from 1,2-addition of alkyllithiums to dialkyl squarates undergo alkene ozonolysis to give β-substituted-α-keto-β-(silyloxy)succinates. With 3-(triethylsilyloxy)butyllithium the methodology was applied to the 2,8-dioxabicyclo[3.2.1]octane core of the squalestatins. Enantioselective 1,2-addition to di-tert-butyl squarate using butyllithium or diethylzinc/Ti(iPrO)4 in the presence of chiral ligands (such as bisoxazolines or camphorsulfonamides, respectively) gave the corresponding tertiary alcohols in up to 67.5:32.5 er. |
| spellingShingle | Sintim, H Valade, A Harling, D Hodgson, D Squarate desymmetrisation–ozonolysis as an approach to β-substituted-α-ketosuccinates and squalestatin synthesis |
| title | Squarate desymmetrisation–ozonolysis as an approach to β-substituted-α-ketosuccinates and squalestatin synthesis |
| title_full | Squarate desymmetrisation–ozonolysis as an approach to β-substituted-α-ketosuccinates and squalestatin synthesis |
| title_fullStr | Squarate desymmetrisation–ozonolysis as an approach to β-substituted-α-ketosuccinates and squalestatin synthesis |
| title_full_unstemmed | Squarate desymmetrisation–ozonolysis as an approach to β-substituted-α-ketosuccinates and squalestatin synthesis |
| title_short | Squarate desymmetrisation–ozonolysis as an approach to β-substituted-α-ketosuccinates and squalestatin synthesis |
| title_sort | squarate desymmetrisation ozonolysis as an approach to β substituted α ketosuccinates and squalestatin synthesis |
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