Dasgupta, A and Bhattacharjee, S and Tong, Z and Guin, A and McNamee, RE and Christensen, KE and Biju, AT and Anderson, EA (2024) Stereoselective Alder-Ene Reactions of Bicyclo1.1.0butanes: Facile Synthesis of Cyclopropyl- and Aryl-Substituted Cyclobutenes. In: Journal of the American Chemical Society, 146 (1). pp. 1196-1203.
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Abstract
Bicyclo1.1.0butanes (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. © 2023 The Authors. Published by American Chemical Society
| Item Type: | Journal Article |
|---|---|
| Publication: | Journal of the American Chemical Society |
| Publisher: | American Chemical Society |
| Additional Information: | The copyright for this article belongs to author |
| Keywords: | Butane; Butenes; Computational chemistry; Propane, Alder-ene reaction; Building blockes; Carbocycles; Cyclobutene; Cyclopropane ring; Cyclopropenes; Cyclopropyl; Facile synthesis; Organic synthesis; Stereo-selective, Stereoselectivity, alkene; alkyne; aryl substituted cyclobutene; bicyclo1.1.0butanes; butane; carbene; carbon; cation; cyclopropane derivative; cyclopropyl; diazoacetates; diazoacetic acid ethyl ester; nucleophile; polycyclic aromatic hydrocarbon derivative; unclassified drug; cyclopropane; cyclopropane derivative; polycyclic aromatic hydrocarbon; vinyl derivative, Article; asymmetric synthesis; broad reaction profile; computational investigation; computer analysis; cyclic voltammetry; cycloaddition; derivatization; organic synthesis; pericyclic process; photochemical carbene generation; photochemistry; reaction analysis; stereoselectivity; ultraviolet visible spectroscopy; X ray crystallography; alder; article; blue light; controlled study; irradiation; nonhuman; signal transduction; stereoselectivity; synthesis |
| Department/Centre: | Others |
| Date Deposited: | 01 Mar 2024 08:52 |
| Last Modified: | 01 Mar 2024 08:52 |
| URI: | https://eprints.iisc.ac.in/id/eprint/83934 |
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