Ammonium-Directed Oxidation of Cyclic Allylic and Homoallylic Amines
We have developed a metal-free and highly diastereoselective ammonium-directed dihydroxylation of 3-aminocyclohex-1-enes upon treatment with Cl 3CCO 2H followed by mCPBA. The reaction mechanism involves protection of the amine...
| Main Authors: | , , |
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| Format: | Journal article |
| Language: | Japanese |
| Published: |
2010
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| _version_ | 1826287121528258560 |
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| author | Kurosawa, W Roberts, P Davies, S |
| author_facet | Kurosawa, W Roberts, P Davies, S |
| author_sort | Kurosawa, W |
| collection | OXFORD |
| description | We have developed a metal-free and highly diastereoselective ammonium-directed dihydroxylation of 3-aminocyclohex-1-enes upon treatment with Cl 3CCO 2H followed by mCPBA. The reaction mechanism involves protection of the amine by protonation, hydrogen-bonded delivery of the oxidant by the allylic ammonium ion formed in situ, followed by highly regioselective ringopening of the intermediate syn-epoxide by trichloroacetic acid, to give a 1,2-anti-2,3syn amino diol after deprotection. Meanwhile, oxidation of the corresponding tertiary amine N-oxide is entirely complementary and proceeds with high anti-diastereoselectivity to afford the corresponding 1,2-anti-2,3-anti amino diol after deprotection, consistent with the epoxidation reaction proceeding under steric or dipole control. The ammonium-directed oxidation protocol is general for a range of cyclic allylic and homoallylic amines and facilitates the metal-free synthesis of all four diastereoisomers of the corresponding 3-amino-1,2-diols, and has recently been employed as one of the key steps in the syntheses of (±)-1- deoxynojirimycin and (±)-1-deoxyaltronojirimycin. |
| first_indexed | 2024-03-07T01:53:53Z |
| format | Journal article |
| id | oxford-uuid:9b0f5ea4-ea47-4c8d-b549-8fd305df398d |
| institution | University of Oxford |
| language | Japanese |
| last_indexed | 2024-03-07T01:53:53Z |
| publishDate | 2010 |
| record_format | dspace |
| spelling | oxford-uuid:9b0f5ea4-ea47-4c8d-b549-8fd305df398d2022-03-27T00:25:51ZAmmonium-Directed Oxidation of Cyclic Allylic and Homoallylic AminesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:9b0f5ea4-ea47-4c8d-b549-8fd305df398dJapaneseSymplectic Elements at Oxford2010Kurosawa, WRoberts, PDavies, SWe have developed a metal-free and highly diastereoselective ammonium-directed dihydroxylation of 3-aminocyclohex-1-enes upon treatment with Cl 3CCO 2H followed by mCPBA. The reaction mechanism involves protection of the amine by protonation, hydrogen-bonded delivery of the oxidant by the allylic ammonium ion formed in situ, followed by highly regioselective ringopening of the intermediate syn-epoxide by trichloroacetic acid, to give a 1,2-anti-2,3syn amino diol after deprotection. Meanwhile, oxidation of the corresponding tertiary amine N-oxide is entirely complementary and proceeds with high anti-diastereoselectivity to afford the corresponding 1,2-anti-2,3-anti amino diol after deprotection, consistent with the epoxidation reaction proceeding under steric or dipole control. The ammonium-directed oxidation protocol is general for a range of cyclic allylic and homoallylic amines and facilitates the metal-free synthesis of all four diastereoisomers of the corresponding 3-amino-1,2-diols, and has recently been employed as one of the key steps in the syntheses of (±)-1- deoxynojirimycin and (±)-1-deoxyaltronojirimycin. |
| spellingShingle | Kurosawa, W Roberts, P Davies, S Ammonium-Directed Oxidation of Cyclic Allylic and Homoallylic Amines |
| title | Ammonium-Directed Oxidation of Cyclic Allylic and Homoallylic Amines |
| title_full | Ammonium-Directed Oxidation of Cyclic Allylic and Homoallylic Amines |
| title_fullStr | Ammonium-Directed Oxidation of Cyclic Allylic and Homoallylic Amines |
| title_full_unstemmed | Ammonium-Directed Oxidation of Cyclic Allylic and Homoallylic Amines |
| title_short | Ammonium-Directed Oxidation of Cyclic Allylic and Homoallylic Amines |
| title_sort | ammonium directed oxidation of cyclic allylic and homoallylic amines |
| work_keys_str_mv | AT kurosawaw ammoniumdirectedoxidationofcyclicallylicandhomoallylicamines AT robertsp ammoniumdirectedoxidationofcyclicallylicandhomoallylicamines AT daviess ammoniumdirectedoxidationofcyclicallylicandhomoallylicamines |