Remote Anodic Substitution of Ketones

James Y. Becker; Larry R. Byrd; Larry L. Miller; Ying Hung So

doi:10.1021/ja00837a027

Remote Anodic Substitution of Ketones

James Y. Becker, Larry R. Byrd, Larry L. Miller, Ying Hung So

Research output: Contribution to journal › Article › peer-review

52 Scopus citations

Abstract

Ketones which lacked branching at the α position were oxidized at ~2.2 V vs. Ag|0.1 M AgNO₃ in acetonitrile. The anolyte was acetonitrile-lithium perchlorate, and the anode was platinum. Substitution of acetamide for hydrogen at remote (γ, δ, ϵ) positions was observed for straight-chain ketones. 2-Hexanone produced 5-acetamido-2-hexanone, 2-heptanone gave mainly 6-acetamido-2-heptanone, and 2-octanone led to a mixture of 5-, 6-, and 7-acetamido-2-octanones. Ketones with branching at the β position gave rearranged ketoamides under these conditions. 4,4-Dimethyl-2-pentanone, for example, gave only 4-acetamido-4-methyl-2-hexanone. The oxidation of 4-deuterio-4-methyl-2-pentanone produced two products: 1-deuterio-2-acetamido-2-methyl-4-pentanone by deuteride migration and 4-deuterio-4-acetamido-2-hexanone by methyl migration. A mechanism involving intramolecular hydrogen abstraction by a ketone cation radical and carbonium ion formation is proposed.

Original language	English
Pages (from-to)	853-856
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	97
Issue number	4
DOIs	https://doi.org/10.1021/ja00837a027
State	Published - 1 Feb 1975
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry (all)
Biochemistry
Colloid and Surface Chemistry

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title = "Remote Anodic Substitution of Ketones",

abstract = "Ketones which lacked branching at the α position were oxidized at ~2.2 V vs. Ag|0.1 M AgNO3 in acetonitrile. The anolyte was acetonitrile-lithium perchlorate, and the anode was platinum. Substitution of acetamide for hydrogen at remote (γ, δ, ϵ) positions was observed for straight-chain ketones. 2-Hexanone produced 5-acetamido-2-hexanone, 2-heptanone gave mainly 6-acetamido-2-heptanone, and 2-octanone led to a mixture of 5-, 6-, and 7-acetamido-2-octanones. Ketones with branching at the β position gave rearranged ketoamides under these conditions. 4,4-Dimethyl-2-pentanone, for example, gave only 4-acetamido-4-methyl-2-hexanone. The oxidation of 4-deuterio-4-methyl-2-pentanone produced two products: 1-deuterio-2-acetamido-2-methyl-4-pentanone by deuteride migration and 4-deuterio-4-acetamido-2-hexanone by methyl migration. A mechanism involving intramolecular hydrogen abstraction by a ketone cation radical and carbonium ion formation is proposed.",

author = "Becker, {James Y.} and Byrd, {Larry R.} and Miller, {Larry L.} and So, {Ying Hung}",

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AU - Becker, James Y.

AU - Byrd, Larry R.

AU - Miller, Larry L.

AU - So, Ying Hung

PY - 1975/2/1

Y1 - 1975/2/1

N2 - Ketones which lacked branching at the α position were oxidized at ~2.2 V vs. Ag|0.1 M AgNO3 in acetonitrile. The anolyte was acetonitrile-lithium perchlorate, and the anode was platinum. Substitution of acetamide for hydrogen at remote (γ, δ, ϵ) positions was observed for straight-chain ketones. 2-Hexanone produced 5-acetamido-2-hexanone, 2-heptanone gave mainly 6-acetamido-2-heptanone, and 2-octanone led to a mixture of 5-, 6-, and 7-acetamido-2-octanones. Ketones with branching at the β position gave rearranged ketoamides under these conditions. 4,4-Dimethyl-2-pentanone, for example, gave only 4-acetamido-4-methyl-2-hexanone. The oxidation of 4-deuterio-4-methyl-2-pentanone produced two products: 1-deuterio-2-acetamido-2-methyl-4-pentanone by deuteride migration and 4-deuterio-4-acetamido-2-hexanone by methyl migration. A mechanism involving intramolecular hydrogen abstraction by a ketone cation radical and carbonium ion formation is proposed.

AB - Ketones which lacked branching at the α position were oxidized at ~2.2 V vs. Ag|0.1 M AgNO3 in acetonitrile. The anolyte was acetonitrile-lithium perchlorate, and the anode was platinum. Substitution of acetamide for hydrogen at remote (γ, δ, ϵ) positions was observed for straight-chain ketones. 2-Hexanone produced 5-acetamido-2-hexanone, 2-heptanone gave mainly 6-acetamido-2-heptanone, and 2-octanone led to a mixture of 5-, 6-, and 7-acetamido-2-octanones. Ketones with branching at the β position gave rearranged ketoamides under these conditions. 4,4-Dimethyl-2-pentanone, for example, gave only 4-acetamido-4-methyl-2-hexanone. The oxidation of 4-deuterio-4-methyl-2-pentanone produced two products: 1-deuterio-2-acetamido-2-methyl-4-pentanone by deuteride migration and 4-deuterio-4-acetamido-2-hexanone by methyl migration. A mechanism involving intramolecular hydrogen abstraction by a ketone cation radical and carbonium ion formation is proposed.

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Remote Anodic Substitution of Ketones

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