Phosphine-Mediated Reductive Insertion of α-Keto Esters and Isatins into Phthalic Anhydride Derivatives,Organic Letters

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Phosphine-Mediated Reductive Insertion of α-Keto Esters and Isatins into Phthalic Anhydride Derivatives
Organic Letters ( IF 4.9 ) Pub Date : 2024-09-09 , DOI: 10.1021/acs.orglett.4c02824
Yuefei Liu ₁ , Qian Liu ₁ , Rongfang Liu ₂ , Xiaoqi Liu ₁ , Hongyu Guo ₁ , Wenjing Yang ₁ , Rong Zhou _{1,

3}

Affiliation

Herein, we report an unprecedented P(NMe₂)₃-mediated reductive insertion of 1,2-dicarbonyl compounds including α-keto esters and isatins into phthalic anhydride-derived alkenes and phthalic anhydrides, which furnishes the corresponding isochroman-1-ones and isochroman-1,4-diones, respectively, in moderate to excellent yields with high chemo- and regioselectivity. Furthermore, the asymmetric version of the ring expansion reaction could be realized by using a chiral auxiliary strategy. Mechanistically, the nucleophilic attack of the Kukhtin-Ramirez adduct, generated from P(NMe₂)₃ and 1,2-dicarbonyl compound, to the anhydride derivative, followed by a cascade ring-opening and ring-closure process, affords the ring expansion product. The reaction represents a novel metal-free carbon insertion ring expansion of aliphatic rings and also the first [1 + 5] annulation involving the Kukhtin-Ramirez adducts.

中文翻译：

膦介导的 α-酮酯和靛红还原插入邻苯二甲酸酐衍生物

在此，我们报道了前所未有的P(NMe ₂ ) ₃介导的1,2-二羰基化合物（包括α-酮酯和靛红）还原插入邻苯二甲酸酐衍生的烯烃和邻苯二甲酸酐中，提供了相应的异色满-1-酮和isochroman-1,4-diones 分别具有中等至优异的产率和高化学选择性和区域选择性。此外，扩环反应的不对称形式可以通过使用手性辅助策略来实现。从机理上讲，由 P(NMe ₂ ) ₃和 1,2-二羰基化合物生成的 Kukhtin-Ramirez 加合物对酸酐衍生物的亲核攻击，随后进行级联开环和闭环过程，从而实现环扩展产品。该反应代表了脂肪族环的新型无金属碳插入环扩展，也是涉及 Kukhtin-Ramirez 加合物的第一个 [1 + 5] 环化。

更新日期：2024-09-09

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