TY - JOUR
T1 - Efficient trapping of ketone enolates with acrylate and β-sulfonylacrylate thioesters, β-sulfonyl, β-sulfinyl- and β-chloro-vinyl ketones; facile preparation of a hydrind-anone, cis-dimethyloctalone, and unsaturated 1, 5-dicarbonyl compounds
AU - Dancer, Robert J.
AU - Haynes, Richard K.
AU - Loughlin, Wendy A.
AU - Vonwilier, Simone C.
PY - 1990
Y1 - 1990
N2 - Tandem conjugate addition-ring closure involving reaction of the lithium enolate arising from conjugate addition of lithiated (E)-but-2-enyldiphenylphosphine oxide to 2-methyl-cyclopent-2-enone with two moles of t-butylthioacrylate generates a hydrindanol, and, in the presence of copper(1), a lactone derived from the hydrindanol. β-Sulfonylacrylate phenyl and t-butyl thioesters, β-chlorovinyl, β-sulfonyl- and β-sulfinyl-vinyI ketones react with the foregoing enolate, and with the enolate generated through conjugate addition of a methylcuprate to 2-methylcyclohexenone to give unsaturated 1, 5-dicarbonyl compounds. The β-chlorovinyl ketones in particular react rapidly and in high yield. 2-Methylcydohexenone has thereby been converted into a cis-dimethyl octalone; the conversion illustrates the effectiveness of β-chlorovinyl methyl ketone in the Robinson annelation. Reactions of the lithium enolate and titanium enol of 2, 6-dimethylcyclohexanone with the β-substituted enones to give the corresponding unsaturated 1, 5-dicarbonyl compounds and other products are also recorded.
AB - Tandem conjugate addition-ring closure involving reaction of the lithium enolate arising from conjugate addition of lithiated (E)-but-2-enyldiphenylphosphine oxide to 2-methyl-cyclopent-2-enone with two moles of t-butylthioacrylate generates a hydrindanol, and, in the presence of copper(1), a lactone derived from the hydrindanol. β-Sulfonylacrylate phenyl and t-butyl thioesters, β-chlorovinyl, β-sulfonyl- and β-sulfinyl-vinyI ketones react with the foregoing enolate, and with the enolate generated through conjugate addition of a methylcuprate to 2-methylcyclohexenone to give unsaturated 1, 5-dicarbonyl compounds. The β-chlorovinyl ketones in particular react rapidly and in high yield. 2-Methylcydohexenone has thereby been converted into a cis-dimethyl octalone; the conversion illustrates the effectiveness of β-chlorovinyl methyl ketone in the Robinson annelation. Reactions of the lithium enolate and titanium enol of 2, 6-dimethylcyclohexanone with the β-substituted enones to give the corresponding unsaturated 1, 5-dicarbonyl compounds and other products are also recorded.
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U2 - 10.1071/CH9901375
DO - 10.1071/CH9901375
M3 - Article
AN - SCOPUS:84970554486
SN - 0004-9425
VL - 43
SP - 1375
EP - 1389
JO - Australian Journal of Chemistry
JF - Australian Journal of Chemistry
IS - 8
ER -