二丁基镁和有机锂试剂介导的亚胺的亲核加成和α-C-H取代反应,Organometallics

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二丁基镁和有机锂试剂介导的亚胺的亲核加成和α-C-H取代反应
Organometallics ( IF 2.5 ) Pub Date : 2021-06-18 , DOI: 10.1021/acs.organomet.0c00815
Yan Dang ₁ , Yalan Wang ₁ , Yafei Li ₁ , Man Xu ₂ , Chaohong Jia ₁ , Yanhua Lu ₁ , Liang Zhang ₁ , Yahong Li ₁ , Yuanzhi Xia ₂

Affiliation

含亚胺配体 2-(2-((((1 H -pyrrol-2-yl)methylene)amino)methyl)-1 H -pyrrol-的一系列亲核加成反应和α-C-H取代反应报道了1-yl) -N , N-二甲基乙烷-1-胺 (HL1)。HL1 分别与 0.5 和 2 当量的ⁿ Bu ₂ Mg 反应得到两种复合物 [Mg(L1) ₂ ] ( 1 ) 和 [Mg ₂ (L2) ₂ ] ( 2 ) (H ₂ L2 = N -((1-(2-(二甲氨基)乙基) -1H-吡咯-2-基)甲基)-1-( 1H-吡咯-2-基)戊-1-胺)。ⁿ Bu ₂ Mg与HL1配体的C=N键的亲核加成发生在形成2的过程中。用 2 和 1 当量的ⁿ BuLi处理 HL1生成 [Li ₂ (L3) ₂ ] ( 3 ) (HL3 = 2-(2-(((1-(1 H -pyrrol-2-yl)pentylidene)amino)甲基) -1H-吡咯-1-基) -N，N-二甲基乙烷-1-胺)和[Li ₂ (L1) ₂ ] ( 4 )。在制备HL1 配体的 HC=NR 部分时发现了由ⁿ BuLi触发的 α-C-H 取代3 . 3的形成展示了 C-C 偶联的新概念，该概念涉及 HC=NR 骨架的惰性 C-H 键活化。HL1 分别与 MeLi、sec -BuLi 和 tert-BuLi 的反应也进行了检查。确定了有机锂试剂与 C=N 键的亲核加成和 HL1 配体的 HC=NR 部分的 α-C-H 取代的产物。DFT 计算使2和3的形成机制合理化。研究了由2催化的硼氢化反应，这些反应具有底物范围广、产率非常好和选择性高的特点。

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Nucleophilic Addition and α-C–H Substitution Reactions of an Imine Mediated by Dibutylmagnesium and Organolithium Reagents

A series of nucleophilic addition reactions and α-C–H substitution reactions of an imine-containing ligand 2-(2-((((1H-pyrrol-2-yl)methylene)amino)methyl)-1H-pyrrol-1-yl)-N,N-dimethylethan-1-amine (HL1) were reported. The reactions of HL1 with 0.5 and 2 equiv of ⁿBu₂Mg, respectively, gave two complexes of compositions [Mg(L1)₂] (1) and [Mg₂(L2)₂] (2) (H₂L2 = N-((1-(2-(dimethylamino)ethyl)-1H-pyrrol-2-yl)methyl)-1-(1H-pyrrol-2-yl)pentan-1-amine). The nucleophilic addition of ⁿBu₂Mg to the C═N bond of the HL1 ligand occurred in the process for the formation of 2. Treatment of HL1 with 2 and 1 equiv of ⁿBuLi generated [Li₂(L3)₂] (3) (HL3 = 2-(2-(((1-(1H-pyrrol-2-yl)pentylidene)amino)methyl)-1H-pyrrol-1-yl)-N,N-dimethylethan-1-amine) and [Li₂(L1)₂] (4). An α-C–H substitution of the HC═NR moiety of the HL1 ligand triggered by ⁿBuLi was discovered in the preparation of 3. The formation of 3 demonstrates a new concept for the C–C coupling that involved inert C–H bond activation of HC═NR skeleton. The reactions of HL1 with MeLi, sec-BuLi, and tert-BuLi, respectively, were also examined. The products for both the nucleophilic addition of organolithium reagents to the C═N bond and α-C–H substitution of the HC═NR moiety of the HL1 ligand were determined. The mechanisms for the formations of 2 and 3 were rationalized by DFT calculations. The hydroboration reactions catalyzed by 2 were investigated, and these reactions characterize ample substrate scope, very good yields, and high selectivity.

更新日期：2021-06-28

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