Chemoselective Union of Olefins, Organohalides, and Redox-Active Esters Enables Regioselective Alkene Dialkylation,Journal of the American Chemical Society

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Chemoselective Union of Olefins, Organohalides, and Redox-Active Esters Enables Regioselective Alkene Dialkylation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-12-11 , DOI: 10.1021/jacs.0c09922
Tao Yang ₁ , Yi Jiang ₁ , Yixin Luo ₂ , Joel Jun Han Lim ₁ , Yu Lan _{2,

3} , Ming Joo Koh ₁

Affiliation

Multicomponent catalytic processes that can generate multiple C(sp3)-C(sp3) bonds in a single step under mild conditions, particularly those that employ inexpensive catalysts and substrates, are highly sought-after in chemistry research for complex molecule synthesis. Here, we disclose an efficient Ni-catalyzed reductive protocol that chemoselectively merges alkenyl amides with two different aliphatic electrophiles. Starting materials are readily accessible from stable and abundant feedstock, and products are furnished in up to >98:2 regioisomeric ratios. The present strategy eliminates the use of sensitive organometallic reagents, tolerates a wide array of complex functionalities, and enables regiodivergent addition of two primary alkyl groups bearing similar electronic and steric attributes across aliphatic C═C bonds with exquisite control of site selectivity. Utility is underscored by the concise synthesis of bioactive compounds and postreaction functionalizations leading to structurally diverse scaffolds. DFT studies revealed that the regiochemical outcome originates from the orthogonal reactivity and chemoselectivity profiles of in situ generated organonickel species.

中文翻译：

烯烃、有机卤化物和氧化还原活性酯的化学选择性结合使区域选择性烯烃二烷基化成为可能

可以在温和条件下一步生成多个 C(sp3)-C(sp3) 键的多组分催化过程，特别是那些使用廉价催化剂和底物的过程，在复杂分子合成的化学研究中备受追捧。在这里，我们公开了一种有效的镍催化还原方案，该方案化学选择性地将烯基酰胺与两种不同的脂肪族亲电试剂合并。起始材料很容易从稳定且丰富的原料中获得，并且产品以高达 >98:2 的区域异构体比例提供。目前的策略消除了敏感有机金属试剂的使用，容忍了广泛的复杂功能，并且能够在脂族 C=C 键上区域发散地添加两个具有相似电子和空间属性的伯烷基，并精确控制位点选择性。生物活性化合物的简洁合成和反应后功能化导致结构多样化的支架强调了实用性。DFT 研究表明，区域化学结果源于原位生成的有机镍物种的正交反应性和化学选择性。

更新日期：2020-12-11

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