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在苯胺存在下，通过二酯氢化制备N-芳族杂环的新途径。

A new route to N-aromatic heterocycles from the hydrogenation of diesters in the presence of anilines.

作者信息

Shi Yiping, Kamer Paul C J, Cole-Hamilton David J, Harvie Michelle, Baxter Emma F, Lim Kate J C, Pogorzelec Peter

机构信息

EaStCHEM , School of Chemistry , University of St. Andrews , St. Andrews , KY16 9ST , Scotland , UK . Email:

出版信息

Chem Sci. 2017 Oct 1;8(10):6911-6917. doi: 10.1039/c7sc01718a. Epub 2017 Aug 8.

DOI:10.1039/c7sc01718a
PMID:29147516
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5636942/
Abstract

The hydrogenation of dicarboxylic acids and their esters in the presence of anilines provides a new synthesis of heterocycles. [Ru(acac)] and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos) gave good to excellent yields of the cyclic amines at 220 °C. When aqueous ammonia was used with dimethyl 1,6-hexadienoic acid, ε-caprolactam was obtained in good yield. A side reaction involving alkylation of the amine by methanol was suppressed by using diesters derived from longer chain and branched alcohols. Hydrogenation of optically pure diesters (dimethyl ()-2-methylbutanedioate and dimethyl ()-2-methylbutanedioate) with aniline afforded racemic 3-methyl-1-phenylpyrrolidine in 78% yield.

摘要

在苯胺存在下对二羧酸及其酯进行氢化反应可提供一种新的杂环合成方法。[Ru(acac)]和1,1,1-三（二苯基膦甲基）乙烷（三膦）在220°C时能给出良好至优异产率的环状胺。当使用氨水与1,6-己二烯二酸二甲酯反应时，能以良好产率得到ε-己内酰胺。通过使用由长链和支链醇衍生的二酯可抑制涉及胺被甲醇烷基化的副反应。光学纯的二酯（()-2-甲基丁二酸二甲酯和()-2-甲基丁二酸二甲酯）与苯胺进行氢化反应可得到外消旋的3-甲基-1-苯基吡咯烷，产率为78%。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/a0fc1d270acd/c7sc01718a-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/742ac3c1a934/c7sc01718a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/3a2b8248bf1e/c7sc01718a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/849cbe375d44/c7sc01718a-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/e099403bce04/c7sc01718a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/a0fc1d270acd/c7sc01718a-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/742ac3c1a934/c7sc01718a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/3a2b8248bf1e/c7sc01718a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/849cbe375d44/c7sc01718a-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/e099403bce04/c7sc01718a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/5636942/a0fc1d270acd/c7sc01718a-s4.jpg

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