分會

第二十四分會：化學(xué)中的量子與經(jīng)典動力學(xué)

摘要

We provide a detailed description of plausible mechanism about IPrAgBr- or IPrAuBr-catalyzed 2-methyl-N-methoxyaniline to obtain multisubstituted aniline[1-2]. This work mainly discusses the rearrangement of methyl and methoxy groups, and hydrogen shift to restore the aromaticity of the benzene via theoretical study. The calculation results show that the [1,3]-methoxy rearrangement in the IPrAgBr catalytic system is the rate-determining step in the entire reaction pathway with energy barrier of ?G?= 29.5 kcal·mol-1, and hydrogen transfer go through a total barrier of ?G?= 28.6 kcal·mol-1. While the result is different from IPrAuBr catalyzed system ([1,3]-methoxy rearrangement ?G?= 28.4 kcal·mol-1; hydrogen shift ?G?= 30.5 kcal·mol-1). Here, the multisubstituted products are different from IPrCuBr catalyzed system[3], resulted from the unstable Ag(III) and Au(III) intermediates. From our computational results, the IPrAg or IPrAu complex is involved in the entire process, whereas substrate-assisted hydrogen shift to restore the aromaticity in the later part can be proceeded without Cu catalyst[4].

關(guān)鍵詞

multisubstituted aniline;[1,3]-methoxy rearrangement;theoretical calculation

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