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Issue 6, 2018
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A palladium-catalyzed dehydrative N-benzylation/C–H benzylation cascade of 2-morpholinoanilines on water

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Abstract

A strategy for the palladium-catalyzed dehydrative tandem benzylation of 2-morpholinoanilines with benzyl alcohols has been developed. This cascade reaction is devised as a straightforward and efficient synthetic route for N-(1,2-diphenylethyl)-2-morpholinoanilines in moderate to good yields (50–81%). The dehydrative sp3 C–H bond benzylation proceeds chemoselectively at the benzylic position of N-benzyl-2-morpholinoaniline to form a new C(sp3)–C (sp3) bond. KIE experiments show that C–H bond activation is involved in the rate-determining step (KIE = 2.7). A Hammett study of 2-morpholinoanilines gives a negative ρ value, suggesting that there is a build-up of positive charge in the transition state. A “on water” protocol, which affords the corresponding desired products with water as the sole co-product, can be achieved under mild reaction conditions without the need for bases or other additives in an atom-economical process.

Graphical abstract: A palladium-catalyzed dehydrative N-benzylation/C–H benzylation cascade of 2-morpholinoanilines on water

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Publication details

The article was received on 18 Dec 2017, accepted on 06 Feb 2018 and first published on 07 Feb 2018


Article type: Paper
DOI: 10.1039/C7GC03780E
Citation: Green Chem., 2018,20, 1297-1305
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    A palladium-catalyzed dehydrative N-benzylation/C–H benzylation cascade of 2-morpholinoanilines on water

    H. Hikawa, R. Ichinose, S. Kikkawa and I. Azumaya, Green Chem., 2018, 20, 1297
    DOI: 10.1039/C7GC03780E

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