Atropisomerism in diarylamines: structural requirements and mechanisms of conformational interconversion
In common with other hindered structures containing two aromatic rings linked by a short tether, diarylamines may exhibit atropisomerism (chirality due to restricted rotation). Previous examples have principally been tertiary amines, especially those with cyclic scaffolds. Little is known of the str...
| Main Authors: | , , , |
|---|---|
| Format: | Journal article |
| Language: | English |
| Published: |
Wiley
2020
|
| _version_ | 1797060694701506560 |
|---|---|
| author | Costil, R Sterling, AJ Duarte Gonzalez, F Clayden, J |
| author_facet | Costil, R Sterling, AJ Duarte Gonzalez, F Clayden, J |
| author_sort | Costil, R |
| collection | OXFORD |
| description | In common with other hindered structures containing two aromatic rings linked by a short tether, diarylamines may exhibit atropisomerism (chirality due to restricted rotation). Previous examples have principally been tertiary amines, especially those with cyclic scaffolds. Little is known of the structural requirement for atropisomerism in structurally simpler secondary and acyclic diarylamines. In this paper we describe a systematic study of a series of acyclic secondary diarylamines, and we quantify the degree of steric hindrance in the ortho positions that is required for atropisomerism to result. Through a detailed experimental and computational analysis, the role of each ortho‐substituent on the mechanism and rate of conformational interconversion is rationalised. We also present a simple predictive model for the design of configurationally stable secondary diarylamines. |
| first_indexed | 2024-03-06T20:20:44Z |
| format | Journal article |
| id | oxford-uuid:2db15486-c2e4-4d25-bbf2-4ad31b85f373 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T20:20:44Z |
| publishDate | 2020 |
| publisher | Wiley |
| record_format | dspace |
| spelling | oxford-uuid:2db15486-c2e4-4d25-bbf2-4ad31b85f3732022-03-26T12:44:40ZAtropisomerism in diarylamines: structural requirements and mechanisms of conformational interconversionJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:2db15486-c2e4-4d25-bbf2-4ad31b85f373EnglishSymplectic ElementsWiley2020Costil, RSterling, AJDuarte Gonzalez, FClayden, JIn common with other hindered structures containing two aromatic rings linked by a short tether, diarylamines may exhibit atropisomerism (chirality due to restricted rotation). Previous examples have principally been tertiary amines, especially those with cyclic scaffolds. Little is known of the structural requirement for atropisomerism in structurally simpler secondary and acyclic diarylamines. In this paper we describe a systematic study of a series of acyclic secondary diarylamines, and we quantify the degree of steric hindrance in the ortho positions that is required for atropisomerism to result. Through a detailed experimental and computational analysis, the role of each ortho‐substituent on the mechanism and rate of conformational interconversion is rationalised. We also present a simple predictive model for the design of configurationally stable secondary diarylamines. |
| spellingShingle | Costil, R Sterling, AJ Duarte Gonzalez, F Clayden, J Atropisomerism in diarylamines: structural requirements and mechanisms of conformational interconversion |
| title | Atropisomerism in diarylamines: structural requirements and mechanisms of conformational interconversion |
| title_full | Atropisomerism in diarylamines: structural requirements and mechanisms of conformational interconversion |
| title_fullStr | Atropisomerism in diarylamines: structural requirements and mechanisms of conformational interconversion |
| title_full_unstemmed | Atropisomerism in diarylamines: structural requirements and mechanisms of conformational interconversion |
| title_short | Atropisomerism in diarylamines: structural requirements and mechanisms of conformational interconversion |
| title_sort | atropisomerism in diarylamines structural requirements and mechanisms of conformational interconversion |
| work_keys_str_mv | AT costilr atropisomerismindiarylaminesstructuralrequirementsandmechanismsofconformationalinterconversion AT sterlingaj atropisomerismindiarylaminesstructuralrequirementsandmechanismsofconformationalinterconversion AT duartegonzalezf atropisomerismindiarylaminesstructuralrequirementsandmechanismsofconformationalinterconversion AT claydenj atropisomerismindiarylaminesstructuralrequirementsandmechanismsofconformationalinterconversion |