Copper-Catalyzed Regiodivergent Internal Allylic Alkylations.
Copper-Catalyzed Regiodivergent Internal Allylic Alkylations.
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铜催化区域发散的内部烯丙基烷基化。
DOI：
10.1002/anie.202304848
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Tambar,UttamK
中科院分区：
文献类型：
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作者：
Manna,MadhuSudan;Yoo,SeokYeol;Sharique,Mohammed;Choi,Hyoju;Pudasaini,Bimal;Baik,Mu-Hyun;Tambar,UttamK
我们报道了一种铜催化的、区域选择性的、立体定向的无偏内烯丙基碳酸酯与官能化烷基和芳基格氏试剂的烷基化反应。在两组铜催化条件下，反应对SN 2或SN 2 ′产物均表现出高度的立体专一性和区域选择性，这使得能够制备具有E-烯烃选择性的多种产物.密度泛函理论计算揭示了基于均铜酸盐和杂铜酸盐不同行为的区域选择性的起源。
We report a copper‐catalyzed, regioselective, and stereospecific alkylation of unbiased internal allylic carbonates with functionalized alkyl and aryl Grignard reagents. The reactions exhibit high stereospecificity and regioselectivity for either SN2 or SN2′ products under two sets of copper‐catalyzed conditions, which enables the preparation of a broad range of products withE‐alkene selectivity. Density functional theory calculations reveal the origins of the regioselectivity based on the different behaviors of homo‐ and heterocuprates.