NOVEL FORMATION OF ISOMERIC BICYCLO[3.2.0]HEPTAN-1-OLS FROM PHENYL VINYL SULFOXIDE AND THE CYCLOPENTANONE LITHIUM ENOLATE GENERATED BY CONJUGATE ADDITION OF LITHIATED (E)-BUT-2-ENYLDIPHENYLPHOSPHINE OXIDE TO 2-METHYLCYCLOPENT-2-ENONE
NOVEL FORMATION OF ISOMERIC BICYCLO[3.2.0]HEPTAN-1-OLS FROM PHENYL VINYL SULFOXIDE AND THE CYCLOPENTANONE LITHIUM ENOLATE GENERATED BY CONJUGATE ADDITION OF LITHIATED (E)-BUT-2-ENYLDIPHENYLPHOSPHINE OXIDE TO 2-METHYLCYCLOPENT-2-ENONE
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DOI：
10.1021/jo00020a018
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发表时间：
1991-09-27
影响因子：
3.6
通讯作者：
HAMBLEY, TW
中科院分区：
文献类型：
--
作者：
HAYNES, RK;LOUGHLIN, WA;HAMBLEY, TW
Whereas the title enolate 2 in THF reacts at -10-degrees-C with 2 equiv of phenyl vinyl sulfone to provide the hydrindanol 9 (9%), it reacts with 1 equiv of phenyl vinyl sulfoxide to give 7-(phenylsulfinyl)bicyclo[3.2.0]heptan-1-ol sulfoxides 11 and 12 (50% overall) and adduct 10 (10%). The yield of the bicycloheptanols decreases to 35% in the dark and increases to 68% under irradiation. Their formation is entirely suppressed by HMPA. Stereochemistry of 12 was provided by X-ray crystallography of the derived sulfone 14. Base-induced ring opening of the sulfone in the presence of phenyl vinyl sulfone gives the alkylated cyclopentanones 17, 18, and 21 and the bicyclo[2.2.1]heptanone 20. The bicyclo[3.2.0]heptanols 11 and 12 are considered to arise by intramolecular nucleophilic or single electron transfer processes.
