Stereoselective Alder-ene reactions of bicyclo[1.1.0]butanes: facile synthesis of cyclopropyl- and aryl-substituted cyclobutenes
Bicyclo[1.1.0]butanes (BCBs), strained carbocycles comprising two fused cyclopropane rings, have become well-established building blocks in organic synthesis, medicinal chemistry, and chemical biology due to their diverse reactivity profile with radicals, nucleophiles, cations, and carbenes. The con...
| Main Authors: | , , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
American Chemical Society
2023
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| _version_ | 1817931745840857088 |
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| author | Dasgupta, A Bhattacharjee, S Tong, Z Guin, A McNamee, RE Christensen, KE Biju, AT Anderson, EA |
| author_facet | Dasgupta, A Bhattacharjee, S Tong, Z Guin, A McNamee, RE Christensen, KE Biju, AT Anderson, EA |
| author_sort | Dasgupta, A |
| collection | OXFORD |
| description | Bicyclo[1.1.0]butanes (BCBs), strained carbocycles comprising two fused cyclopropane rings, have become well-established building blocks in organic synthesis, medicinal chemistry, and chemical biology due to their diverse reactivity profile with radicals, nucleophiles, cations, and carbenes. The constraints of the bicyclic ring system confer high p-character on the interbridgehead C–C bond, leading to this broad reaction profile; however, the use of BCBs in pericyclic processes has to date been largely overlooked in favor of such stepwise, non-concerted additions. Here, we describe the use of BCBs as substrates for ene-like reactions with strained alkenes and alkynes, which give rise to cyclobutenes decorated with highly substituted cyclopropanes and arenes. The former products are obtained from highly stereoselective reactions with cyclopropenes, generated in situ from vinyl diazoacetates under blue light irradiation (440 nm). Cyclobutenes featuring a quaternary aryl-bearing carbon atom are prepared from equivalent reactions with arynes, which proceed in high yields under mild conditions. Mechanistic studies highlight the importance of electronic effects in this chemistry, while computational investigations support a concerted pathway and rationalize the excellent stereoselectivity of reactions with cyclopropenes. |
| first_indexed | 2024-12-09T03:26:54Z |
| format | Journal article |
| id | oxford-uuid:f6f6f28f-7cda-4acb-8a35-efb65ff59731 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-12-09T03:26:54Z |
| publishDate | 2023 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:f6f6f28f-7cda-4acb-8a35-efb65ff597312024-11-29T15:15:27ZStereoselective Alder-ene reactions of bicyclo[1.1.0]butanes: facile synthesis of cyclopropyl- and aryl-substituted cyclobutenesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:f6f6f28f-7cda-4acb-8a35-efb65ff59731EnglishSymplectic ElementsAmerican Chemical Society2023Dasgupta, ABhattacharjee, STong, ZGuin, AMcNamee, REChristensen, KEBiju, ATAnderson, EABicyclo[1.1.0]butanes (BCBs), strained carbocycles comprising two fused cyclopropane rings, have become well-established building blocks in organic synthesis, medicinal chemistry, and chemical biology due to their diverse reactivity profile with radicals, nucleophiles, cations, and carbenes. The constraints of the bicyclic ring system confer high p-character on the interbridgehead C–C bond, leading to this broad reaction profile; however, the use of BCBs in pericyclic processes has to date been largely overlooked in favor of such stepwise, non-concerted additions. Here, we describe the use of BCBs as substrates for ene-like reactions with strained alkenes and alkynes, which give rise to cyclobutenes decorated with highly substituted cyclopropanes and arenes. The former products are obtained from highly stereoselective reactions with cyclopropenes, generated in situ from vinyl diazoacetates under blue light irradiation (440 nm). Cyclobutenes featuring a quaternary aryl-bearing carbon atom are prepared from equivalent reactions with arynes, which proceed in high yields under mild conditions. Mechanistic studies highlight the importance of electronic effects in this chemistry, while computational investigations support a concerted pathway and rationalize the excellent stereoselectivity of reactions with cyclopropenes. |
| spellingShingle | Dasgupta, A Bhattacharjee, S Tong, Z Guin, A McNamee, RE Christensen, KE Biju, AT Anderson, EA Stereoselective Alder-ene reactions of bicyclo[1.1.0]butanes: facile synthesis of cyclopropyl- and aryl-substituted cyclobutenes |
| title | Stereoselective Alder-ene reactions of bicyclo[1.1.0]butanes: facile synthesis of cyclopropyl- and aryl-substituted cyclobutenes |
| title_full | Stereoselective Alder-ene reactions of bicyclo[1.1.0]butanes: facile synthesis of cyclopropyl- and aryl-substituted cyclobutenes |
| title_fullStr | Stereoselective Alder-ene reactions of bicyclo[1.1.0]butanes: facile synthesis of cyclopropyl- and aryl-substituted cyclobutenes |
| title_full_unstemmed | Stereoselective Alder-ene reactions of bicyclo[1.1.0]butanes: facile synthesis of cyclopropyl- and aryl-substituted cyclobutenes |
| title_short | Stereoselective Alder-ene reactions of bicyclo[1.1.0]butanes: facile synthesis of cyclopropyl- and aryl-substituted cyclobutenes |
| title_sort | stereoselective alder ene reactions of bicyclo 1 1 0 butanes facile synthesis of cyclopropyl and aryl substituted cyclobutenes |
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