One-Step Synthesis of delta-Lactones Having Biological Activity by Remote Carbonylation

远程羰基化一步合成具有生物活性的δ-内酯

• 批准号: 06453137
• 负责人: RYU Ilhyong
• 金额: $ 0.58万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453137/
• 关键词: delta-lactone; carbon monoxide; saturated alcohol; radical carbonylation; lead tetraacetate; remote functionalization; 1,5 hydrogen shift; alkoxy radical

In this work, a novel straightforward method for the synthesis of delta-lactones has been pursued. Taking advantage of the lead tetraacetate-induced oxidation of alcohols, a novel delta-lactone synthesis from saturated alcohols and CO was achieved. This remote carbonylation is quite general for primary and secondary alcohols whose delta-carbons are primary or secondary. In case of an alcohol having both primary and secondary delta-carbons, carbon monoxide is incorporated at the secondary carbon in a 24 : 1 ratio. The reaction sequence can be successfully applied to a one-step synthesis of a carpenter bee sex pheromone starting from commercially available, optically pure (R)-(-)-2-hexanol and carbon monoxide. On the other hand, attempted reaction of a 1,2-diol type substrate resulted in beta-fragmentation rather than carbonylation. This suggests that for an application of this remote carbonylation to the synthesis of mevalonolactone, beta-hydroxy group should be introduced after constructing the key delta-lactone skeleton.

在这项工作中，已经采用了一种新颖的直接方法来合成三角洲 - 内酯。利用四乙酸铅诱导的醇的氧化，获得了一种新型的Delta-Lactone从饱和醇和CO进行的合成。对于初级和二级醇的偏远羰基化是一般的，其三角洲 - 碳碳是主要的或次要的。如果酒精具有初级和次级三角洲 - 碳酸盐，则一氧化碳在次级碳中以24：1的比例掺入。反应序列可以成功应用于木匠蜜蜂性信息素的一步合成，从市售，光学纯净（R） - （ - ） - 2-己醇和一氧化碳。另一方面，1,2-二醇类型底物的尝试反应导致β-裂片而不是羰基化。这表明，对于将这种远程羰基化应用于甲瓦隆酮的合成中，应在构造键的Delta-lactone骨架后引入β-羟基。

项目成果

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