A Lewis Acid-Catalyzed Diastereoselective Synthesis of Functionalized 2-Diazo-1,5-dicarbonyl Compounds
A Lewis Acid-Catalyzed Diastereoselective Synthesis of Functionalized 2-Diazo-1,5-dicarbonyl Compounds
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DOI：
10.1021/acscatal.1c03036
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发表时间：
2021-09
期刊：
影响因子：
12.9
通讯作者：
Evan M. Howard;M. Brewer
中科院分区：
文献类型：
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作者：
Evan M. Howard;M. Brewer
在路易斯酸催化下，烯氧基硅烷与β-羟基-α-重氮羰基反应生成了一系列不同的2-重氮基-1，5-二羰基化合物。该反应通过锌(OTf)2催化的β-羟基-α-重氮羰基的脱羟基反应生成乙烯基重氮离子中间体，该中间体被环氧硅烷亲核试剂截留，得到分子复杂性增加的含重氮骨架。该反应似乎是普遍的，各种官能团，包括共同的保护基团，是很好的耐受性。2-重氮-1，5-二羰基产物以高达99%的产率形成，非对映选择性高达>；20：1。
A diverse array of 2-diazo-1,5-dicarbonyl compounds were formed by the Lewis acid-catalyzed reaction of enoxysilanes with β-hydroxy-α-diazo carbonyls. This reaction proceeds via the Zn(OTf)2-catalyzed dehydroxylation of the β-hydroxy-α-diazo carbonyl to form a vinyl diazonium ion intermediate that is intercepted by the enoxysilane nucleophile to give diazo-containing scaffolds with increased molecular complexity. The reaction appears to be general, and a variety of functional groups, including common protecting groups, are well tolerated. The 2-diazo-1,5-dicarbonyl products are formed in yields of up to 99% with diastereoselectivity up to >20:1.