期刊
RSC ADVANCES
卷 11, 期 34, 页码 20961-20969出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1ra02399c
关键词
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资金
- National Natural Science Foundation of China [21542011]
- Yibin University [2021QH03]
- Scientific Research Fund of Sichuan Provincial Education Department [17ZA0196]
- Science and Technology Planning Project of Leshan Science and Technology Bureau [18JZD118]
- Leshan Normal University [Z1601]
A study on the mechanism of B(C6F5)(3) catalyzed imine reduction under stoichiometric water conditions revealed four novel pathways induced by (C6F5)(3)B-OH2, different from previous mechanisms. These pathways involve nucleophilic water or amine catalysis and explain the experimental results.
A DFT and experimental study on the mechanism of B(C6F5)(3) catalyzed imine reduction is performed using PhSiH3 as reductant under stoichiometric water conditions. Ingleson's path B is reconfirmed here. And four novel (C6F5)(3)B-OH2 induced pathways (paths C2, C3, D2 and D3) entirely different from all the previous mechanisms were determined for the first time. They are all B(C6F5)(3) and water/amine catalyzed cycles, in which the nucleophilic water or amine catalyzed addition step between PhSiH3 and the N-silicon amine cation is the rate-determining step of paths C2/D2 and C3/D3 with activation Gibbs free energy barriers of 23.9 and 18.3 kcal mol(-1) in chloroform, respectively, while the final desilylation of the N-silicon amine cation depends on an important intermediate, (C6F5)(3)B-OH-. The competitive behavior of the 5 paths can explain the experimental facts perfectly; if all the reactants and catalysts are added into the system simultaneously, water amount and nucleophiles (excess water and produced/added amine) provide on-off selectivity of the pathways and products. 1 eq. water leads to quick formation of (C6F5)(3)B-OH-, leading to B-II being turned off, and nucleophiles like excess water and produced/added amine switch on CD-II, leading to production of the amine. B-I ' of Ingleson's path B is the only mechanism for anhydrous systems, giving N-silicon amine production only; B-I and C-I are competitive paths for systems with no more than 1 eq. water, producing the N-silicon amine and the [PhHC = NHPh](+)[(C6F5)(3)B-OH](-) ion pair; and paths C2, C3, D2 and D3 are competitive for systems with 1 eq. water and nucleophiles like excess water or added/produced amine, directly giving amination products.
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