Electron-transfer catalyzed cycloaddition reactions of unactivated cyclic olefins in weakly coordinating anion electrolyte

Michael P. Stewart, Kevin Lam, Daesung Chong, William E. Geiger

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Cis-Cyclooctene, C8H14, undergoes an efficient electron-transfer (ET) catalyzed cycloaddition reaction in dichloromethane containing [NBu4][B(C6F5)4] as supporting electrolyte. The reactions were initiated by in-situ anodic generation of catalytic amounts of either [N(2,4-C6H3Br2)3]+ (1+, "magic green") or [ReCp(CO)3]+ (2+, Cp = (η5-C5H5)). The olefin radical chain reaction induced by ET mediation was complete in less than 10 min, some 100-1000 times faster than the optimum photochemically induced preparations of cyclobutane derivatives from cyclic olefins. Yields of up to 87% of mixtures of C16H28 isomers were obtained at an electro-synthetic level. Use of the weakly coordinating [B(C6F5)4]- anion, rather than a traditional small anion such as [PF6]- or [ClO4]-, was required to carry out the cyclization reactions. The more easily oxidized trans-cyclooctene, when anodized directly at an electrode, gave a similar isomeric mixture of cyclobutanes. Cycloheptene and cyclohexene underwent similar [2 + 2] coupling to give cyclobutane products. Cyclopentene gave a [2 + 2 + 2] cyclized trimer. The mechanism appears to involve a key radical-substrate propagation step in which an olefin radical cation reacts with a neutral olefin to give a cyclobutyl radical cation, which then accepts an electron, most likely from another olefin, to form the final neutral compound. Although the E1/2 potentials of the ET mediators are 660-900 mV lower than the estimated oxidation potentials of the olefins, the endergonic nature of the ET initiation step works to the advantage of the chain process by favoring the radical-substrate propagation step.

Original languageEnglish
Pages (from-to)68-77
Number of pages10
JournalJournal of Electroanalytical Chemistry
Volume743
DOIs
Publication statusPublished - Apr 15 2015
Externally publishedYes

Fingerprint

Cycloparaffins
Cycloaddition
Alkenes
Electrolytes
Olefins
Anions
Cyclobutanes
Negative ions
Electrons
Cations
Cyclopentanes
Positive ions
Methylene Chloride
Cyclization
Substrates
Carbon Monoxide
Isomers
Dichloromethane
Derivatives
Oxidation

Keywords

  • Cyclic olefins
  • Cyclooctene
  • Electrolyte anions
  • Radical cation
  • Radical-substrate reaction
  • Tetrakis(perfluoroaryl)borate anion

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Analytical Chemistry
  • Electrochemistry

Cite this

Electron-transfer catalyzed cycloaddition reactions of unactivated cyclic olefins in weakly coordinating anion electrolyte. / Stewart, Michael P.; Lam, Kevin; Chong, Daesung; Geiger, William E.

In: Journal of Electroanalytical Chemistry, Vol. 743, 15.04.2015, p. 68-77.

Research output: Contribution to journalArticle

Stewart, Michael P. ; Lam, Kevin ; Chong, Daesung ; Geiger, William E. / Electron-transfer catalyzed cycloaddition reactions of unactivated cyclic olefins in weakly coordinating anion electrolyte. In: Journal of Electroanalytical Chemistry. 2015 ; Vol. 743. pp. 68-77.
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abstract = "Cis-Cyclooctene, C8H14, undergoes an efficient electron-transfer (ET) catalyzed cycloaddition reaction in dichloromethane containing [NBu4][B(C6F5)4] as supporting electrolyte. The reactions were initiated by in-situ anodic generation of catalytic amounts of either [N(2,4-C6H3Br2)3]+ (1+, {"}magic green{"}) or [ReCp(CO)3]+ (2+, Cp = (η5-C5H5)). The olefin radical chain reaction induced by ET mediation was complete in less than 10 min, some 100-1000 times faster than the optimum photochemically induced preparations of cyclobutane derivatives from cyclic olefins. Yields of up to 87{\%} of mixtures of C16H28 isomers were obtained at an electro-synthetic level. Use of the weakly coordinating [B(C6F5)4]- anion, rather than a traditional small anion such as [PF6]- or [ClO4]-, was required to carry out the cyclization reactions. The more easily oxidized trans-cyclooctene, when anodized directly at an electrode, gave a similar isomeric mixture of cyclobutanes. Cycloheptene and cyclohexene underwent similar [2 + 2] coupling to give cyclobutane products. Cyclopentene gave a [2 + 2 + 2] cyclized trimer. The mechanism appears to involve a key radical-substrate propagation step in which an olefin radical cation reacts with a neutral olefin to give a cyclobutyl radical cation, which then accepts an electron, most likely from another olefin, to form the final neutral compound. Although the E1/2 potentials of the ET mediators are 660-900 mV lower than the estimated oxidation potentials of the olefins, the endergonic nature of the ET initiation step works to the advantage of the chain process by favoring the radical-substrate propagation step.",
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AB - Cis-Cyclooctene, C8H14, undergoes an efficient electron-transfer (ET) catalyzed cycloaddition reaction in dichloromethane containing [NBu4][B(C6F5)4] as supporting electrolyte. The reactions were initiated by in-situ anodic generation of catalytic amounts of either [N(2,4-C6H3Br2)3]+ (1+, "magic green") or [ReCp(CO)3]+ (2+, Cp = (η5-C5H5)). The olefin radical chain reaction induced by ET mediation was complete in less than 10 min, some 100-1000 times faster than the optimum photochemically induced preparations of cyclobutane derivatives from cyclic olefins. Yields of up to 87% of mixtures of C16H28 isomers were obtained at an electro-synthetic level. Use of the weakly coordinating [B(C6F5)4]- anion, rather than a traditional small anion such as [PF6]- or [ClO4]-, was required to carry out the cyclization reactions. The more easily oxidized trans-cyclooctene, when anodized directly at an electrode, gave a similar isomeric mixture of cyclobutanes. Cycloheptene and cyclohexene underwent similar [2 + 2] coupling to give cyclobutane products. Cyclopentene gave a [2 + 2 + 2] cyclized trimer. The mechanism appears to involve a key radical-substrate propagation step in which an olefin radical cation reacts with a neutral olefin to give a cyclobutyl radical cation, which then accepts an electron, most likely from another olefin, to form the final neutral compound. Although the E1/2 potentials of the ET mediators are 660-900 mV lower than the estimated oxidation potentials of the olefins, the endergonic nature of the ET initiation step works to the advantage of the chain process by favoring the radical-substrate propagation step.

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