Issue 3, 2018

Nickel-catalyzed difunctionalization of allyl moieties using organoboronic acids and halides with divergent regioselectivities

Abstract

Efficient difunctionalization of alkenes allows the rapid construction of molecular complexity from simple building blocks in organic synthesis. We present herein a nickel-catalyzed dicarbofunctionalization of alkenes using readily available organoboronic acids and organic halides in a three-component fashion. In particular, an unprecedented regioselectivity of the 1,3-dicarbofunctionalization of N-allylpyrimidin-2-amine is achieved when aryl and methyl iodides are utilized. In contrast, the use of alkyl bromides with β-hydrogens results in 1,3-hydroarylation or oxidative 1,3-diarylation. Preliminary mechanistic studies suggest an isomerization involving nickel hydride in the 1,3-difunctionalization reactions. On the other hand, the use of alkenyl or alkynyl halides promotes alternative regioselectivities to deliver 1,2-alkenylcarbonation or intriguing 2,1-alkynylcarbonation products. Such 2,1-alkynylarylation is also applicable to N-allylbenzamide as a different class of substrates. Overall, this nickel-catalyzed process proves to be powerful in delivering versatile difunctionalized compounds using readily available reagents/catalysts and a simple procedure.

Graphical abstract: Nickel-catalyzed difunctionalization of allyl moieties using organoboronic acids and halides with divergent regioselectivities

Supplementary files

Article information

Article type
Edge Article
Submitted
19 Jul 2017
Accepted
25 Oct 2017
First published
26 Oct 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 600-607

Nickel-catalyzed difunctionalization of allyl moieties using organoboronic acids and halides with divergent regioselectivities

W. Li, J. K. Boon and Y. Zhao, Chem. Sci., 2018, 9, 600 DOI: 10.1039/C7SC03149A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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