13C Nuclear Magnetic Resonance Studies. Part 48.13C Spectra of a Variety of Bicyclic Ketones
作者:
S. H. Grover,
D. H. Marr,
J. B. Stothers,
C. T. Tan,
期刊:
Canadian Journal of Chemistry
(NRC Available online 1975)
卷期:
Volume 53,
issue 9
页码: 1351-1361
ISSN:0008-4042
年代: 1975
DOI:10.1139/v75-187
出版商: NRC Research Press
数据来源: NRC
摘要:
The13C n.m.r. spectra of a series of 37 bicyclic ketones have been recorded to examine the variations in13C shieldings with structure and with methyl substitution. Several examples of six skeletal types were included: bicyclo[4.4.0]decanones, bicyclo[4.1.0]heptanones, bicyclo-[3.1.0]hexanones, bicyclo[3.2.2]nonanones, bicyclo[3.2.1]- and -[3.3.0]octanones as well as bicyclo[2.1.1]hexan-2-one, nopinone (6,6-dimethylbicyclo[3.1.1]heptan-2-one), and two methyl derivatives of the latter. The observed trends associated with methyl substitution follow well-defined patterns and offer further support for the application of13C shieldings as aids for stereochemical assignments especially through the well known γ effects. The variation in the shieldings of the carbonyl carbons in these systems suggested that bond eclipsing interactions have an important influence on this parameter. With this notion, the heretofore puzzling variations observed for the cycloalkanones are readily interprétable in terms of their favored conformations.
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