Recommanded Product: 2097273-59-9In 2020, Liu, Yanhong;Yang, Yiying;Zhu, Rongxiu;Zhang, Dongju published 《Computational Clarification of Synergetic RuII/CuI-Metallaphotoredox Catalysis in C(sp3)-N Cross-Coupling Reactions of Alkyl Redox-Active Esters with Anilines》. 《ACS Catalysis》published the findings. The article contains the following contents:
The C-N coupling of alkyl electrophiles for amine synthesis is a less-developed area in comparison with that of aryl electrophiles largely because of the difficulty in product-generating C(sp3)-N reductive elimination. The recent work by Hu et al. developed an effective strategy for the C-N coupling of alkyl redox-active esters with anilines by merging photoredox catalysis and copper catalysis with an oxoacetic acid ligand (LH2). Here, we present a DFT-based computational study to understand how the special dual catalysis works in a cooperative fashion with the assistance of the ligand. Photoredox catalysis is found to occur most possibly through an oxidative quenching mechanism (RuII/*RuII/RuIII/RuII) with Et3N as the quencher rather than with the exptl. proposed copper complex. Copper catalytic cycle (CuI/CuII/CuIII/CuI) is predicted to proceed via a CuI-oxidation-first pathway instead of the hypothetical aniline-deprotonation-first pathway in the experiment, and the most likely catalytic active species is identified as the CuILH complex. With the RuII/CuI-metallaphotoredox catalysis, the most feasible mechanism for the C(sp3)-N cross-coupling involves six steps: (i) generation of cyclohexyl radical (Cy•) via the single electron transfer (SET) from photoexcited *RuII to the complex of redox-active ester with CuI, (ii) coordination of aniline to CuI center, (iii) Cy• radical addition to CuI center, (iv) SET between CuII-cyclohexyl aniline complex and generated Et3N•+, (v) deprotonation of aniline, and (vi) reductive elimination of the CuIII-cyclohexyl amido intermediate to produce the C(sp3)-N coupling product. The CuI complex is identified to play a dual role in the title reaction, which acts as the promoter in oxidative quenching process and as the catalyst in the copper catalytic cycle. To complete the study, the researchers used 2,6-Dimethoxyanilino(oxo)acetic acid (cas: 2097273-59-9) .
2,6-Dimethoxyanilino(oxo)acetic acid is one of ethers-buliding-blocks. Ethers feature bent C–O–C linkages. In dimethyl ether, the bond angle is 111° and C–O distances are 141 pm. The barrier to rotation about the C–O bonds is low. Recommanded Product: 2097273-59-9 The bonding of oxygen in ethers, alcohols, and water is similar. In the language of valence bond theory, the hybridization at oxygen is sp3.
Reference:
Ether – Wikipedia,
Ether | (C2H5)2O – PubChem