Highly Efficient Suzuki-Miyaura Polymerization Enabled by Direct Transmetalation with Boronic Esters [0.03%]
直接利用硼酸酯进行转金属化催化的高效Suzuki-Miyaura聚合反应
Haigen Xiong,Yu Lu,Qijie Lin et al.
Haigen Xiong et al.
Experimental and theoretical investigations revealed that direct transmetalation of boronic esters without prior conversion to more reactive intermediates plays a critical role in this protocol, thus avoiding the problematic deboronation associated with unstable boronic acids....Keywords: Conjugated polymers; Suzuki-Miyaura coupling; direct transmetalation of boronic esters; polymerization methodology. © 2025 Wiley‐VCH GmbH.
Reductively Induced Aryl Transmetalation: An Alternative Catalytically Relevant Ni-Catalyzed Biaryl Coupling Mechanism [0.03%]
还原性诱导的芳基转金属化：Ni催化的联芳烃偶联反应的一个替代催化机理
Antonio Romero-Arenas,Mihai V Popescu,McKenna K Goetz et al.
Antonio Romero-Arenas et al.
Here, we provide evidence for a previously unrecognized pathway involving reductively induced transmetalation between NiI(Ar) and NiII(Ar)X species....Experimental and computational data show that the NiI-to-NiII transmetalation mechanism is much more favorable than NiII-to-NiII transmetalation....The NiII(2-tolyl)2 product of NiI-to-NiII transmetalation is stable at room temperature, while sterically less encumbered NiII(Ar)2 species undergo rapid reductive elimination to afford biaryl and a Ni0 byproduct....The latter species can serve as a source of electrons to promote further transmetalation and biaryl formation....Addition of catalytic quantities of a cobaltocene-based reductant eliminates the induction period and accelerates biaryl formation, consistent with the NiI-to-NiII transmetalation pathway.
Divergent Asymmetric Dialkylation of Dienoic Acids with Carbonyls and Zinc Reagents via Tandem Ni(0) and Ni(II) Catalysis [0.03%]
通过镍(0)和镍(II)催化串联 catalysis实现富马酸酯与羰基及锌试剂的发散性不对称二官能团化反应
Shun-Zhong Tan,Dai-Fu Zhang,Lei Zhu et al.
Shun-Zhong Tan et al.
After transmetalation with another organometallic reagent, the resultant alkyl allylic nickel(II) species readily undertake reductive elimination to finally forge two C(sp3)-C(sp3) bonds, even with switchable diastereodivergence and α,β- or α,δ-regiodivergence via ligand or substrate control.
Gold(I) complexes with NHC ligands functionalized with sulfoxide groups: Design, synthesis, in vitro studies and insights into the mechanism of action as anticancer drugs [0.03%]
含硫氧化物基团的NHC配体金(I)配合物的设计、合成及体外研究和作为抗肿瘤药物的作用机制研究
Eleonora Zampieri,Chiara Donati,Victoria Mechrouk et al.
Eleonora Zampieri et al.
The corresponding gold(I) complexes [AuCl(NHC)] were isolated by transmetalation reaction from the silver complex to the [AuCl(SMe2)] precursor. The employed NHC ligands are characterized by benzyl and CH2CH2S(O)R (R = Ph or t-Bu) groups as nitrogen wingtip substituents.
Transition-Metal-Free, Intramolecular Oxidative Coupling of C(sp3)-B with C(sp2)-H [0.03%]
无需过渡金属参与的C(sp3)-B与C(sp2)-H的分子内氧化偶联反应
Tingting Dan,Yuling Liu,Lai Li et al.
Tingting Dan et al.
Additionally, the propensity for β-hydride elimination further complicates the transmetalation process, limiting their applicability in synthetic transformations.
Mechanistic insights into base-free nickel-catalyzed Suzuki-Miyaura cross-coupling of acid fluoride and the origin of chemoselectivity: a DFT study [0.03%]
无碱镍催化酸氟芳烃的Suzuki-Miyaura交叉偶联反应机理及化学选择性的起源：基于DFT的研究
Wasihun Menberu Dagnaw,Yohannes Mulugeta Hailu,Ahmed M Mohammed
Wasihun Menberu Dagnaw
The coupling reaction proceeds via four stages: (1) oxidative addition of the acid fluoride to the Ni(0) center to break the C-F bond, (2) transmetalation with diboron reagent, (3) carbonyl deinsertion via reverse carbonyl migratory insertion, and (4) reductive elimination to afford the coupling product...Furthermore, our computational results indicate that transmetalation prefers a concerted mechanism. Detailed analyses reveals that the strong fluorophilicity of boron enables efficient, base-free transmetalation.
Arpan De,Brandon Lu,Yoel P Ohayon et al.
Arpan De et al.
Here a generalized method is presented for tuning the local band structure of DNA using transmetalation in metal-mediated base pairs (mmDNA).
On-surface chemistry of Pb(II) tetraphenylporphyrin on Au(111): reversible metalation, thermal degradation, and formation of a covalent organic framework [0.03%]
金Pb(II)四苯基卟啉的表面化学：可逆金属化，热降解及共价有机骨架结构的形成
Jan Herritsch,Cong Guo,Lukas J Heuplick et al.
Jan Herritsch et al.
Thermal degradation of Pb(TPP) on Au(111) differs mechanistically from previously reported transmetalation on Cu(111). Below 550 K, the Pb atom in Pb(TPP) is replaced by hydrogen through demetalation, resulting in a reduction of the released Pb atom and formation of H2(TPP).
Wei Liu,Dajiang Huang,Junnian Wei et al.
Wei Liu et al.
synthetic strategies: (i) transmetalation, which has been employed to prepare RE metallacyclopentadienes and spiro-metallacyclopentadienes, which, featuring various ligand systems, provide distinct coordination environments around the RE center, significantly influencing their reactivity, and (ii) transmetalation
Wenjun Tang,Jianxun Huang,Chao Pei et al.
Wenjun Tang et al.
DFT calculation revealed a NaBr-bridged downstream transmetalation and the importance of noncovalent interaction in controlling the enantioselectivity.
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