Indolyne and aryne distortions and nucleophilic regioselectivites.
Density functional theory computations reproduce the surprisingly high regioselectivities in nucleophilic additions and cycloadditions to 4,5-indolynes and the low regioselectivities in the reactions of 5,6-indolynes. Transition-state distortion energies control the regioselectivities, activating th...
| Main Authors: | , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
2010
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| _version_ | 1797068377002344448 |
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| author | Cheong, P Paton, R Bronner, S Im, G Garg, N Houk, K |
| author_facet | Cheong, P Paton, R Bronner, S Im, G Garg, N Houk, K |
| author_sort | Cheong, P |
| collection | OXFORD |
| description | Density functional theory computations reproduce the surprisingly high regioselectivities in nucleophilic additions and cycloadditions to 4,5-indolynes and the low regioselectivities in the reactions of 5,6-indolynes. Transition-state distortion energies control the regioselectivities, activating the 5 and 6 positions over the 4 and 7 positions, leading to high preferences for 5- and 6-substituted products from 4,5- and 6,7-indolynes, respectively. Orbital and electrostatic interactions have only minor effects, producing low regioselectivities in the reactions of 5,6-indolynes. The distortion model predicts high regioselectivities with 6,7-indolynes; these have been verified experimentally. The regioselectivities found with other arynes are explained on the basis of distortion energies that are reflected in reactant geometries. |
| first_indexed | 2024-03-06T22:09:53Z |
| format | Journal article |
| id | oxford-uuid:51719e09-8298-4bd9-a40b-a933dfae596f |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T22:09:53Z |
| publishDate | 2010 |
| record_format | dspace |
| spelling | oxford-uuid:51719e09-8298-4bd9-a40b-a933dfae596f2022-03-26T16:19:35ZIndolyne and aryne distortions and nucleophilic regioselectivites.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:51719e09-8298-4bd9-a40b-a933dfae596fEnglishSymplectic Elements at Oxford2010Cheong, PPaton, RBronner, SIm, GGarg, NHouk, KDensity functional theory computations reproduce the surprisingly high regioselectivities in nucleophilic additions and cycloadditions to 4,5-indolynes and the low regioselectivities in the reactions of 5,6-indolynes. Transition-state distortion energies control the regioselectivities, activating the 5 and 6 positions over the 4 and 7 positions, leading to high preferences for 5- and 6-substituted products from 4,5- and 6,7-indolynes, respectively. Orbital and electrostatic interactions have only minor effects, producing low regioselectivities in the reactions of 5,6-indolynes. The distortion model predicts high regioselectivities with 6,7-indolynes; these have been verified experimentally. The regioselectivities found with other arynes are explained on the basis of distortion energies that are reflected in reactant geometries. |
| spellingShingle | Cheong, P Paton, R Bronner, S Im, G Garg, N Houk, K Indolyne and aryne distortions and nucleophilic regioselectivites. |
| title | Indolyne and aryne distortions and nucleophilic regioselectivites. |
| title_full | Indolyne and aryne distortions and nucleophilic regioselectivites. |
| title_fullStr | Indolyne and aryne distortions and nucleophilic regioselectivites. |
| title_full_unstemmed | Indolyne and aryne distortions and nucleophilic regioselectivites. |
| title_short | Indolyne and aryne distortions and nucleophilic regioselectivites. |
| title_sort | indolyne and aryne distortions and nucleophilic regioselectivites |
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