Medium-ring Ketone Synthesis. Intramolecular Acylation of Sulfur-stabilized Carbanions : A Model Study

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概要

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• Intramoleclar acylation of the sulfur-stabilized carbanions of the acyclic ester 9 and amide sulfides 11 was carried out as a model study for developing an effective method for the construction of medium-ring ketones by ring closure. Reaction of 9a-c or 11a-g with lithium diisopropylamide (LDA) proceeded smoothly and the expected keto sulfides 10a-c or 12a-g, respectively, were obtained. In the cases where R_1 and/or R_2 in 11 were normal alkyl groups, the reaction did not take place. However, these difficulties were readily overcome either by introducing a methyl group next to the carbonyl group or by converting the sulfides into the corresponding sulfoxides or sulfones. Acylation in the allyl sulfides 11b, d, f and the allyl sulfone 20b takes place at the α-position to the sulfur atom, yielding β, γ-unsaturated ketones. A reductive removal of the sulfide moiety or its conversion into other functional groups was also examined.

• 公益社団法人日本薬学会の論文
• 1983-02-25

著者

• 大石 武

  Faculty Of Engineering Yokohama National University:(present Address)meiji College Of Pharmacy

• 大石 武

  The Institute of Physical and Chemical Research (Riken)

• 大塚 晏央

  Faculty Of Engineering Yokohama National University:(present Address)pharmaceutical Research Center

• 大塚 晏央

  The Institute of Physical and Chemical Research (Riken)

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