Oxyallyl Cation Capture via Electrophilic Deborylation of Organoboronates: Access to α , α ′-Substituted Cyclic Ketones
Oxyallyl Cation Capture via Electrophilic Deborylation of Organoboronates: Access to α , α ′-Substituted Cyclic Ketones
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通过有机硼酸盐的亲电脱硼酸捕获氧丙烯基阳离子：获得 α 、α α-取代的环酮
DOI：
10.1021/acs.orglett.9b02831
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发表时间：
2019
期刊：
影响因子：
5.2
通讯作者：
May, Jeremy A.
中科院分区：
文献类型：
--
作者：
Nguyen, Truong N.;Setthakarn, Krit;May, Jeremy A.
介绍了一种合成α，α‘-取代环酮的新方法，即通过有机硼酸盐与α-羟基硅烯醇醚的亲核加成反应。反应通过C(Sp2)和C(Sp)硼酸盐的亲电脱氧反应捕获原位生成的氧烯丙基阳离子而进行。这种高效和直接的方法提供了直接获得α取代的硅烯醇醚的方法，产率高，具有完全的区域选择性。一锅法脱硅提供了相应的α，α‘-二取代酮，具有高的非对映选择性。
An umpolung strategy to synthesizeα,α′-substituted cyclic ketones through the nucleophilic addition of organoboronates toα-hydroxyl silyl enol ethers is described. The reaction proceeds via the trapping of in situ generated oxyallyl cations via the electrophilic deborylation of C(sp2) and C(sp) borates. This efficient and straightforward method provides direct access toα-substituted silyl enol ethers in high yield with complete regioselectivity. Desilylation in a one-pot procedure provides the correspondingα,α′-disubstituted ketones with high diastereoselectivity.