How and Why Does Ni0 Promote Smooth Etheric C?O Bond Cleavage and C?C Bond Formation? A Theoretical Study,Chemistry - A European Journal

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How and Why Does Ni0 Promote Smooth Etheric C?O Bond Cleavage and C?C Bond Formation? A Theoretical Study
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2015-08-20 , DOI: 10.1002/chem.201502114
Hiroyuki Ogawa _{1,

2} , Hiroki Minami _{1,

2} , Takashi Ozaki _{1,

2} , Shinsuke Komagawa _{2,

3} , Chao Wang _{1,

2} , Masanobu Uchiyama _{1,

2}

Affiliation

Ni‐catalyzed cross‐coupling between aryl alkyl ethers (ArOR) and Grignard reagents (RMgBr), known since 1979, proceeds under mild conditions in many cases. Although the reaction routes of various synthetic protocols involving transition‐metal‐catalyzed CO bond activation have been elucidated, the mechanism of this etheric Kumada–Tamao–Curriu reaction remains enigmatic. This is because oxidative addition of inert etheric CO to Ni⁰ is thermodynamically and kinetically unfavorable, making it hard to explain the observed high reactivity of ether toward Ni catalysts. In this work, we used DFT calculations to identify a plausible reaction pathway by the Ni⁰‐ate complex, which enables smooth CO bond cleavage and R‐group transfer with reasonable activation barriers; this mechanism also accounts for the ineffectiveness of Pd catalysts. These results throw new light on both CO activation and cross‐coupling, and should be valuable for further rational development of the methodologies.

中文翻译：

Ni0如何以及为何促进平滑的醚C ？O键解理和C ？C键形成？理论研究

自1979年以来，镍在芳基烷基醚（ArOR）和格氏试剂（RMgBr）之间的镍催化交叉偶联在许多情况下在温和条件下进行。虽然涉及过渡金属催化的C ^各种合成协议的反应路线 O键激活已被阐明，此醚熊田-玉尾-Curriu反应的机理仍然是不清楚。这是因为惰性醚CO在Ni ^0上的氧化加成在热力学和动力学上都是不利的，这使得难以解释所观察到的醚对Ni催化剂的高反应性。在这项工作中，我们使用DFT计算通过将Ni，以确定一个合理的反应途径⁰ -ate复杂，这使得能够平滑Ç O键裂解和R基团转移具有合理的激活障碍; 该机制也解释了钯催化剂的无效性。这些结果为CO的活化和交叉耦合提供了新的思路，对于进一步合理地开发方法学将是有价值的。

更新日期：2015-08-20

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