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Issue 21, 2018
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Intramolecular alkene hydroamination and degradation of amidines: divergent behavior of rare earth metal amidinate intermediates

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Abstract

Direct N–H addition of amidines to alkenes is a highly valuable but challenging transformation that remains elusive. Now, the intramolecular hydroamidination of N-alkenylamidines is achieved by using a rare earth catalyst, which provides an efficient and atom-economical approach for substituted imidazolines and tetrahydropyrimidines. Moreover, a mild and efficient method for the catalytic degradation of amidines to give amines and nitriles is also developed. Additionally, amidine reconstruction followed by an intramolecular alkene hydroamidination strategy for the synthesis of substituted imidazolines and tetrahydropyrimidines from secondary enamines and inactive amidines has also been established, which may circumvent the need for some unavailable starting materials. The mechanistic studies prove that these reactions proceed via a key lanthanide amidinate intermediate that can undergo substrate- and amine-controlled chemodivergent transformations: intramolecular alkene insertion, nitrile extrusion, amidinate reconstruction, or a combination of the reactions. The results presented here not only demonstrate the synthetic potential and versatility of alkene hydroamidination with substrates, but also provide a good insight into the factors that promote or deter the hydroamidination of alkenes.

Graphical abstract: Intramolecular alkene hydroamination and degradation of amidines: divergent behavior of rare earth metal amidinate intermediates

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Publication details

The article was received on 18 Jul 2018, accepted on 11 Sep 2018 and first published on 14 Sep 2018


Article type: Paper
DOI: 10.1039/C8CY01481G
Citation: Catal. Sci. Technol., 2018,8, 5573-5581
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    Intramolecular alkene hydroamination and degradation of amidines: divergent behavior of rare earth metal amidinate intermediates

    D. Zhang, R. Liu and X. Zhou, Catal. Sci. Technol., 2018, 8, 5573
    DOI: 10.1039/C8CY01481G

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