Synthesis and molecular desighn of biological active aromadendrane type of sesquiterpenes

生物活性芳香型倍半萜的合成与分子设计

• 批准号: 04671285
• 负责人: HARAYAMA Takashi
• 金额: $ 1.41万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04671285/
• 关键词: aromadendrane; sesquiterpene; bicyclo [5.1.0] octane; higher order orqanocuprate; dibromocyclopropane; differential substitution reaction; ミブロモシクロプロパン; ビシロク[5.1.0]オクタン; ジブロモシクロプロパン; ワンポット反応; ジブロモカルベン; ディックマン反応; セレソ化合物

1.Improved synthesis of 2-carbomethoxycyclohept-2-en-1-onIt was clearly found that a high dilution method was not necessary for synthesis of the title compound as reported previously.2.Synthesis of 8,8-dimethylbicyclo [5.1.0] octanes from 8,8-dibromobicyclo [5.1.0] octanes Higher order organocuprate Prepared from commercially avialable methyl lithium and cuprous cyanide was very effective for the synthesis of title compound.3.One-pot unsymmetrical double substitution of 8,8-dibromobicyclo [5.1.0] octane and its stereochemistryA differential substitution reaction of dibromocyclopropane in one-pot using higher order organocuprate-allyl bromide gave a desired product in a moderate chemical yield and stereo-selectivity. Its stereochemistry was deduced by the reaction mechanism and by chemical means.4.Synthesis 8,8-dimethylbicyclo [5.1.0] octenoneReaction of 8,8-dimethylbicyclo [5.1.0] octanone with phenylselenyl chloride followed by oxidation with hydrogene peroxide gave octenone derivative in a good yield.

1. 2-甲氧羰基环庚-2-烯-1-酮的改进合成清楚地发现，合成标题化合物不需要如以前报道的高度稀释法。2.从8，8-二溴双环[5.1.0]以市售的甲基锂和氰化亚铜为原料，合成了辛烷类有机铜化合物，3.8，8-二溴双环[5.1.0]辛烷的一锅不对称双取代反应及其立体化学在一锅反应中，用高阶有机铜酸盐-烯丙基溴进行二溴环丙烷的差示取代反应，以中等的化学产率和立体选择性得到了目标产物。8，8-二甲基双环[5.1.0]辛烯酮的合成8，8-二甲基双环[5.1.0]辛烯酮与氯化苯硒反应，再用过氧化氢氧化，以较好的收率得到辛烯酮衍生物。