A [4+4] annulation strategy for the synthesis of eight-membered carbocycles based on intramolecular cycloadditions of conjugated enynes
A [4+4] annulation strategy for the synthesis of eight-membered carbocycles is reported that proceeds via a cascade involving two pericyclic processes. In the first step, the [4+2] cycloaddition of a conjugated enyne with an electron-deficient cyclobutene generates a strained six-membered cyclic all...
| Main Authors: | , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
Elsevier
2015
|
| Online Access: | http://hdl.handle.net/1721.1/99488 https://orcid.org/0000-0002-9812-206X |
| _version_ | 1811092633960841216 |
|---|---|
| author | Robinson, Julia M. Tlais, Sami F. Fong, Jennie Danheiser, Rick Lane |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Robinson, Julia M. Tlais, Sami F. Fong, Jennie Danheiser, Rick Lane |
| author_sort | Robinson, Julia M. |
| collection | MIT |
| description | A [4+4] annulation strategy for the synthesis of eight-membered carbocycles is reported that proceeds via a cascade involving two pericyclic processes. In the first step, the [4+2] cycloaddition of a conjugated enyne with an electron-deficient cyclobutene generates a strained six-membered cyclic allene that isomerizes to the corresponding 1,3-cyclohexadiene. In the second step, this bicyclo[4.2.0]octa-2,4-diene intermediate undergoes thermal or acid-promoted 6-electron electrocyclic ring opening to furnish a 2,4,6-cyclooctatrienone. The latter transformation represents the first example of the promotion of 6-electron electrocyclic ring opening reactions by acid. |
| first_indexed | 2024-09-23T15:21:11Z |
| format | Article |
| id | mit-1721.1/99488 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T15:21:11Z |
| publishDate | 2015 |
| publisher | Elsevier |
| record_format | dspace |
| spelling | mit-1721.1/994882022-09-29T14:25:26Z A [4+4] annulation strategy for the synthesis of eight-membered carbocycles based on intramolecular cycloadditions of conjugated enynes Robinson, Julia M. Tlais, Sami F. Fong, Jennie Danheiser, Rick Lane Massachusetts Institute of Technology. Department of Chemistry Robinson, Julia M. Tlais, Sami F. Fong, Jennie Danheiser, Rick Lane A [4+4] annulation strategy for the synthesis of eight-membered carbocycles is reported that proceeds via a cascade involving two pericyclic processes. In the first step, the [4+2] cycloaddition of a conjugated enyne with an electron-deficient cyclobutene generates a strained six-membered cyclic allene that isomerizes to the corresponding 1,3-cyclohexadiene. In the second step, this bicyclo[4.2.0]octa-2,4-diene intermediate undergoes thermal or acid-promoted 6-electron electrocyclic ring opening to furnish a 2,4,6-cyclooctatrienone. The latter transformation represents the first example of the promotion of 6-electron electrocyclic ring opening reactions by acid. National Institutes of Health (U.S.) (GM 28273) Pfizer Inc. National Science Foundation (U.S.). Graduate Research Fellowship AstraZeneca (Firm) (Graduate Fellowship) David A. Johnson Summer Graduate Fellowship 2015-10-28T13:22:47Z 2015-10-28T13:22:47Z 2011-09 2011-09 Article http://purl.org/eprint/type/JournalArticle 00404020 http://hdl.handle.net/1721.1/99488 Robinson, Julia M., Sami F. Tlais, Jennie Fong, and Rick L. Danheiser. “A [4+4] Annulation Strategy for the Synthesis of Eight-Membered Carbocycles Based on Intramolecular Cycloadditions of Conjugated Enynes.” Tetrahedron 67, no. 51 (December 2011): 9890–9898. https://orcid.org/0000-0002-9812-206X en_US http://dx.doi.org/10.1016/j.tet.2011.09.031 Tetrahedron Creative Commons Attribution-Noncommercial-NoDerivatives http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf Elsevier OAPOT |
| spellingShingle | Robinson, Julia M. Tlais, Sami F. Fong, Jennie Danheiser, Rick Lane A [4+4] annulation strategy for the synthesis of eight-membered carbocycles based on intramolecular cycloadditions of conjugated enynes |
| title | A [4+4] annulation strategy for the synthesis of eight-membered carbocycles based on intramolecular cycloadditions of conjugated enynes |
| title_full | A [4+4] annulation strategy for the synthesis of eight-membered carbocycles based on intramolecular cycloadditions of conjugated enynes |
| title_fullStr | A [4+4] annulation strategy for the synthesis of eight-membered carbocycles based on intramolecular cycloadditions of conjugated enynes |
| title_full_unstemmed | A [4+4] annulation strategy for the synthesis of eight-membered carbocycles based on intramolecular cycloadditions of conjugated enynes |
| title_short | A [4+4] annulation strategy for the synthesis of eight-membered carbocycles based on intramolecular cycloadditions of conjugated enynes |
| title_sort | 4 4 annulation strategy for the synthesis of eight membered carbocycles based on intramolecular cycloadditions of conjugated enynes |
| url | http://hdl.handle.net/1721.1/99488 https://orcid.org/0000-0002-9812-206X |
| work_keys_str_mv | AT robinsonjuliam a44annulationstrategyforthesynthesisofeightmemberedcarbocyclesbasedonintramolecularcycloadditionsofconjugatedenynes AT tlaissamif a44annulationstrategyforthesynthesisofeightmemberedcarbocyclesbasedonintramolecularcycloadditionsofconjugatedenynes AT fongjennie a44annulationstrategyforthesynthesisofeightmemberedcarbocyclesbasedonintramolecularcycloadditionsofconjugatedenynes AT danheiserricklane a44annulationstrategyforthesynthesisofeightmemberedcarbocyclesbasedonintramolecularcycloadditionsofconjugatedenynes AT robinsonjuliam 44annulationstrategyforthesynthesisofeightmemberedcarbocyclesbasedonintramolecularcycloadditionsofconjugatedenynes AT tlaissamif 44annulationstrategyforthesynthesisofeightmemberedcarbocyclesbasedonintramolecularcycloadditionsofconjugatedenynes AT fongjennie 44annulationstrategyforthesynthesisofeightmemberedcarbocyclesbasedonintramolecularcycloadditionsofconjugatedenynes AT danheiserricklane 44annulationstrategyforthesynthesisofeightmemberedcarbocyclesbasedonintramolecularcycloadditionsofconjugatedenynes |