Copper-catalyzed asymmetric allylic alkylation of racemic inert cyclic allylic ethers under batch and flow conditions,Chemical Science

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Copper-catalyzed asymmetric allylic alkylation of racemic inert cyclic allylic ethers under batch and flow conditions
Chemical Science ( IF 7.6 ) Pub Date : 2023-03-22 , DOI: 10.1039/d3sc00127j
Jun Li ₁ , Xiao Song ₁ , Yan Wang ₁ , Junrong Huang _{1,

2} , Hengzhi You _{1,

2} , Fen-Er Chen _{1,

2,

3}

Affiliation

Highly enantioselective Cu-catalyzed asymmetric allylic alkylation of racemic inert cyclic allylic ethers is accomplished in this work. The use of Grignard reagents in combination with BF₃·OEt₂ and CuBr·SMe₂/L2 is the key to enable employment of long-challenging low reactive allylic substrates in this AAA reaction. In addition, the approach exhibited a remarkable superiority in the construction of a stereogenic center involving challenging sterically hindered nucleophiles for both primary and secondary alkyl groups. Extension of this method under continuous flow conditions was also performed with excellent enantioselectivity in a short residence time. Mechanistic experiments indicated that the reaction proceeded through an in situ generated allylic bromide intermediate. All these advantages demonstrated that this chiral catalytic system is a valuable complement for existing asymmetric catalytic methods.

中文翻译：

批次和流动条件下外消旋惰性环烯丙基醚的铜催化不对称烯丙基烷基化

在这项工作中完成了外消旋惰性环烯丙基醚的高对映选择性 Cu 催化的不对称烯丙基烷基化。_{将格氏试剂与 BF 3} ·OEt ₂和 CuBr·SMe ₂ / L2结合使用是在该 AAA 反应中使用长期具有挑战性的低反应性烯丙基底物的关键。此外，该方法在构建立体中心方面表现出显着的优势，该中心涉及对伯烷基和仲烷基的空间位阻亲核试剂的挑战。该方法在连续流动条件下的扩展也在短停留时间内以优异的对映选择性进行。机理实验表明该反应通过原位生成烯丙基溴中间体。所有这些优点表明，这种手性催化体系是对现有不对称催化方法的一个有价值的补充。

更新日期：2023-03-22

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