Electrochemical preparation of bicyclobutanes and other strained cycloalkanes

Rifi, M. R.

doi:10.1021/ja00993a035

Cited by 72 publications

(21 citation statements)

References 21 publications

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“…In the first step for the reduction of 1,4-pentadiene, an electron can add to either double bond to give a radical-anion, with the electron having a tendency to reside preferentially on a terminal methylene carbon (-CHzCHCH2CH=CH~); using the computer program MOPAC (Version 6.00) which uses the AM1 Hamiltonian, we calculated that one-electron reduction of 1,4-pentadiene results in an electron density of -0.43 on the terminal methylene carbon, -0.26 on the methine carbon, and -0.02 on the internal methylene carbon. Protonation can then occur at the terminal methylene carbon to yield a neutral radical (CH3CHCH2CH=CH2) which is further reduced to a secondary carbanion (reaction [1][2][3][4][5][6][7][8][9][10][11][12][13][14]; this secondary carbanion can be protonated to give 1-pentene (reaction [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] or can rearrange (reaction 1-15) before being protonated to form cis-or trans-2-pentene.…”

Section: Methodsmentioning

confidence: 99%

Electrochemical Reduction of 1,5‐Dihalopentanes at Carbon Cathodes in Dimethylformamide

Pritts

Peters

1994

J. Electrochem. Soc.

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Studies of the electrochemical reduction of 1,5-dibromo-, 1,5-diiodo-, 1-bromo-5-chloro-, and 1-ch]oro-5-iodopentane at carbon electrodes in dimethylformamide containing tetramethylammonium perchlorate have been carried out with cyclic voltammetry and controlled-potential electrolysis. Cyclopentane, arising from the intramolecular cyclization of an electrogenerated 5-halopent-l-yl carbanion, is a significant electrolysis product. Moreover, depending on the identity of the 1,5-dihalopentane and the presence or absence of a proton source, one can obtain substantial yields of n-pentane, 1-pentene, 1-chloropentane, and 1,10-dichlorodecane as well as smaller amounts of cis-and trans-2-pentene, 5-chloro-1-pentene, 1,4-pentadiene, n-decane, 1-decene, n-pentadecane, 1-pentadecene, and n-eicosane. Experiments involving the use of several different deuterium ion or atom donors have been employed to determine the pathways by which these products are formed. In addition, we offer some comparisons concerning the electrochemical behavior of 1,3-dihalopropanes, 1,4-dihalobutanes, and 1,5-diha]opentanes at carbon cathodes.Only a limited amount of research concerning the electrochemistry of 1,5-dihalopentanes has been published, all of which pertains to the electrochemical reduction of 1,5-dibromopentane at mercury cathodes. 1-~ In a polarographic study of the reduction of 1,5-dibromopentane in dimethylformamide containing tetramethylammonium bromide and 5% water, Z~vada et al. 1 concluded that the starting material is reduced in a pair of two-electron steps which cannot be resolved into discrete waves. Rift 2'3 investigated the electrolytic reduction of 1,5-dibromopentane at a mercury pool in dimethylformamide containing tetra-n-butylammonium perehlorate and postulated that n-pentane is produced through a carbanion mechanism. However, different results were reported by Casanova and Rogers, ~ who found that controlled-potential electrolysis of 1,5-dibromopentane at mercury in dimethylformamide containing various tetraalkylammonium salts afforded a dialkylmercury species (CsHIoHgC~HI0) in high yield, whereas constant-current electrolysis of the same starting material gave only n-pentane. Avaca et al. ~ examined the electrochemical behavior of 1,5-dibromopentane in dimethyliormamide or acetonitrile containing various tetraalkylammonium salts at a mercury cathode and observed that controlled-potential eleetrolyses yielded mercury-containing solids with the general formula (C~HIoHg)~.In this paper we discuss the electrochemical reductions of 1,5-dibromo-, 1,5-diiodo-, l-bromo-5-ehloro-, and lchloro-5-iodopentane at carbon cathodes in dimethylformamide containing tetramethylammonium perehlorate; the electrochemistry of the last three 1,5-dihalopentanes has not been described previously. In performing this work, we have avoided the possible formation of organomercury compounds by not using mercury cathodes. We report for the first time the occurrence of electroreduetive intramolecular eyclization of each of the four 1,5-dihalopenfanes ...

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Section: Methodsmentioning

confidence: 99%

Electrochemical Reduction of 1,5‐Dihalopentanes at Carbon Cathodes in Dimethylformamide

Pritts

Peters

1994

J. Electrochem. Soc.

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“…The strategy was recently expanded to alkynes (Scheme 43). [148] Electrochemical versions of the Wurtz reaction have been utilized to intramolecularly form strained ring systems from alkyl halides under cathodic conditions, with bicyclobutane [149] and spiropentane [150] being two classic examples (Scheme 44). In a similar fashion, intermolecular cross-coupling of dihalide compounds and alkenes have been demonstrated to results in cyclopropane products in both direct [151] and metal-catalyzed [152] protocols.…”

Section: Electroreductive Removal Of Functional Groupsmentioning

confidence: 99%

Organic Electrosynthesis: Applications in Complex Molecule Synthesis

2019

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Organic electrosynthesis is an enabling and sustainable technology, which constitutes a rapidly expanding field of research. Electrochemical approaches serve as convenient and green alternatives to stoichiometric and toxic chemical redox agents. Electrosynthesis constitutes a promising platform for harnessing the unique reactivity profiles of radical intermediates, expediting the development of new reaction manifolds. This Review highlights both anodic and cathodic methods for the construction of various kinds of complex molecules.

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“…Commercially available tris(trimethylsilyl)silane (Aldrich), tert-butyl peroxide (Aldrich), chlorine (Aldrich), aqueous ammonia (Fisher Scientific), and phosphorus pentoxide (Fisher Scientific) were used without purification. The syntheses of 1, [40] 1,3-Cl 2 -1, [41] 1,3-Br 2 -1, [42] 1,3-I 2 -1, [43] 1,3-(CN) 2 -1, [44] 1,3-Br 2 -2,2-Cl 2 -1, [45] 1,3-Br 2 -2, [30] and 1,3-I 2 -2 [30] were reported previously.…”

Section: Reagentsmentioning

confidence: 99%

Coupling between Substituents as a Function of Cage Structure: Synthesis and Valence Ionized States of Bridgehead Disubstituted Parent and Hexafluorinated Bicyclo[1.1.1]pentane Derivatives C₅X₆Y₂

Ehara

Fukawa

Nakatsuji

et al. 2007

Chemistry An Asian Journal

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He(I) photoelectron spectroscopy was used to examine the valence-shell electronic structure of three new and seven previously known bicyclo[1.1.1]pentane derivatives, 1,3-Y2-C5X6 (for X = H, Y = H, Cl, Br, I, CN; for X = F, Y = H, Br, I, CN). A larger series (X = H or F, Y = H, F, Cl, Br, I, At, CN) has been studied computationally with the SAC-CI (symmetry-adapted cluster configuration interaction) method. The outer-valence ionization spectra calculated by the SAC-CI method, including spin-orbit interaction, reproduced the experimental photoelectron spectra well, and quantitative assignments are given. When the extent of effective through-cage interaction between the bridgehead halogen lone-pair orbitals was defined in the usual way by orbital-energy splitting, it was found to be larger than that mediated by other cages such as cubane, and was further enhanced by hexafluorination. The origin of the orbital-energy splitting is analyzed in terms of cage structure, and it is pointed out that its relation to the degree of interaction between the bridgehead substituents is not as simple as is often assumed.

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Electrochemical preparation of bicyclobutanes and other strained cycloalkanes

Cited by 72 publications

References 21 publications

Electrochemical Reduction of 1,5‐Dihalopentanes at Carbon Cathodes in Dimethylformamide

Electrochemical Reduction of 1,5‐Dihalopentanes at Carbon Cathodes in Dimethylformamide

Organic Electrosynthesis: Applications in Complex Molecule Synthesis

Coupling between Substituents as a Function of Cage Structure: Synthesis and Valence Ionized States of Bridgehead Disubstituted Parent and Hexafluorinated Bicyclo[1.1.1]pentane Derivatives C₅X₆Y₂

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Electrochemical preparation of bicyclobutanes and other strained cycloalkanes

Cited by 72 publications

References 21 publications

Electrochemical Reduction of 1,5‐Dihalopentanes at Carbon Cathodes in Dimethylformamide

Electrochemical Reduction of 1,5‐Dihalopentanes at Carbon Cathodes in Dimethylformamide

Organic Electrosynthesis: Applications in Complex Molecule Synthesis

Coupling between Substituents as a Function of Cage Structure: Synthesis and Valence Ionized States of Bridgehead Disubstituted Parent and Hexafluorinated Bicyclo[1.1.1]pentane Derivatives C5X6Y2

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Coupling between Substituents as a Function of Cage Structure: Synthesis and Valence Ionized States of Bridgehead Disubstituted Parent and Hexafluorinated Bicyclo[1.1.1]pentane Derivatives C₅X₆Y₂