Intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins.
Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo...
| Main Authors: | , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
2007
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| _version_ | 1797100531853819904 |
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| author | Hodgson, D Chung, Y Nuzzo, I Freixas, G Kulikiewicz, K Cleator, E Paris, J |
| author_facet | Hodgson, D Chung, Y Nuzzo, I Freixas, G Kulikiewicz, K Cleator, E Paris, J |
| author_sort | Hodgson, D |
| collection | OXFORD |
| description | Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]hexan-2-ols via Sn-Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g-7.5 kg) synthesis of bicyclo[3.1.0]hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-beta-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation. |
| first_indexed | 2024-03-07T05:38:53Z |
| format | Journal article |
| id | oxford-uuid:e4e4ff0e-0250-4f22-9235-233fd6de55d0 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T05:38:53Z |
| publishDate | 2007 |
| record_format | dspace |
| spelling | oxford-uuid:e4e4ff0e-0250-4f22-9235-233fd6de55d02022-03-27T10:19:46ZIntramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:e4e4ff0e-0250-4f22-9235-233fd6de55d0EnglishSymplectic Elements at Oxford2007Hodgson, DChung, YNuzzo, IFreixas, GKulikiewicz, KCleator, EParis, JLithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]hexan-2-ols via Sn-Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g-7.5 kg) synthesis of bicyclo[3.1.0]hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-beta-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation. |
| spellingShingle | Hodgson, D Chung, Y Nuzzo, I Freixas, G Kulikiewicz, K Cleator, E Paris, J Intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins. |
| title | Intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins. |
| title_full | Intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins. |
| title_fullStr | Intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins. |
| title_full_unstemmed | Intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins. |
| title_short | Intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins. |
| title_sort | intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins |
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