Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals. An experimental and theoretical study

G A  DiLabio; K U  Ingold; M D  Roydhouse; J C  Walton

doi:10.1021/ol0481683

Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals. An experimental and theoretical study

G A DiLabio, K U Ingold, M D Roydhouse, J C Walton

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

Abstract

Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals gave distinct EPR spectra thanks to surprisingly large beta-hydrogen atom hyperfine splittings that enabled them to be characterized and monitored. DFT computations indicated that the axial species (X = CH2) had a higher barrier to rotation about the (O)C-alpha-C-beta bond. The computed difference DeltaHdegrees for the axial and equatorial radicals (R = H, X CH2) was 0.8 kcal mol(-1).

Original language	English
Pages (from-to)	4319-4322
Number of pages	4
Journal	Organic Letters
Volume	6
DOIs	https://doi.org/10.1021/ol0481683
Publication status	Published - 11 Nov 2004

Keywords

ELECTRON-SPIN-RESONANCE
CYCLOALKYLMETHYL RADICALS
PARAMAGNETIC RESONANCE
ACYL RADICALS
CONFORMATIONAL-ANALYSIS
ORGANIC-CHEMISTRY
CARBON-MONOXIDE
ALKYL RADICALS
SIGMA-RADICALS
ALLYLSTANNANES

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10.1021/ol0481683

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title = "Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals. An experimental and theoretical study",

abstract = "Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals gave distinct EPR spectra thanks to surprisingly large beta-hydrogen atom hyperfine splittings that enabled them to be characterized and monitored. DFT computations indicated that the axial species (X = CH2) had a higher barrier to rotation about the (O)C-alpha-C-beta bond. The computed difference DeltaHdegrees for the axial and equatorial radicals (R = H, X CH2) was 0.8 kcal mol(-1).",

keywords = "ELECTRON-SPIN-RESONANCE, CYCLOALKYLMETHYL RADICALS, PARAMAGNETIC RESONANCE, ACYL RADICALS, CONFORMATIONAL-ANALYSIS, ORGANIC-CHEMISTRY, CARBON-MONOXIDE, ALKYL RADICALS, SIGMA-RADICALS, ALLYLSTANNANES",

author = "DiLabio, {G A} and Ingold, {K U} and Roydhouse, {M D} and Walton, {J C}",

year = "2004",

month = nov,

day = "11",

doi = "10.1021/ol0481683",

language = "English",

volume = "6",

pages = "4319--4322",

journal = "Organic Letters",

issn = "1523-7060",

publisher = "American Chemical Society (ACS)",

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TY - JOUR

T1 - Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals. An experimental and theoretical study

AU - DiLabio, G A

AU - Ingold, K U

AU - Roydhouse, M D

AU - Walton, J C

PY - 2004/11/11

Y1 - 2004/11/11

N2 - Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals gave distinct EPR spectra thanks to surprisingly large beta-hydrogen atom hyperfine splittings that enabled them to be characterized and monitored. DFT computations indicated that the axial species (X = CH2) had a higher barrier to rotation about the (O)C-alpha-C-beta bond. The computed difference DeltaHdegrees for the axial and equatorial radicals (R = H, X CH2) was 0.8 kcal mol(-1).

AB - Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals gave distinct EPR spectra thanks to surprisingly large beta-hydrogen atom hyperfine splittings that enabled them to be characterized and monitored. DFT computations indicated that the axial species (X = CH2) had a higher barrier to rotation about the (O)C-alpha-C-beta bond. The computed difference DeltaHdegrees for the axial and equatorial radicals (R = H, X CH2) was 0.8 kcal mol(-1).

KW - ELECTRON-SPIN-RESONANCE

KW - CYCLOALKYLMETHYL RADICALS

KW - PARAMAGNETIC RESONANCE

KW - ACYL RADICALS

KW - CONFORMATIONAL-ANALYSIS

KW - ORGANIC-CHEMISTRY

KW - CARBON-MONOXIDE

KW - ALKYL RADICALS

KW - SIGMA-RADICALS

KW - ALLYLSTANNANES

UR - http://www.scopus.com/inward/record.url?scp=9444277149&partnerID=8YFLogxK

U2 - 10.1021/ol0481683

DO - 10.1021/ol0481683

M3 - Article

SN - 1523-7060

VL - 6

SP - 4319

EP - 4322

JO - Organic Letters

JF - Organic Letters

ER -

Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals. An experimental and theoretical study

Abstract

Keywords

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