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. 2016 Feb 1;7(2):1383-1387.
doi: 10.1039/c5sc03903g. Epub 2015 Nov 11.

β-Arylation of oxime ethers using diaryliodonium salts through activation of inert C(sp)-H bonds using a palladium catalyst

Jing Peng  1 , Chao Chen  1 , Chanjuan Xi  1
Affiliations

β-Arylation of oxime ethers using diaryliodonium salts through activation of inert C(sp)-H bonds using a palladium catalyst

Jing Peng et al. Chem Sci. .

Abstract

An efficient method of selective β-arylation of oxime ethers was realized by using a palladium catalyst with diaryliodonium salts as the key arylation reagents. The reaction proceeded smoothly through the activation of inert C(sp3)-H bonds to give corresponding ketones and aldehydes. This convenient procedure can be successfully applied to construct new C(sp3)-C(sp2) bonds on a number of complex molecules derived from natural products and thus serves as a practical synthetic tool for direct late-stage C(sp3)-H functionalization.

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Figures

Scheme 1
Scheme 1. Pd-catalyzed β-arylation reaction of oxime ethers via C(sp3)–H bond activation.
Scheme 2
Scheme 2. Scope of diaryliodonium salts to form desired β-arylated products.
Scheme 3
Scheme 3. β-Arylation of selected oxime ethers with 2d.
Scheme 4
Scheme 4. The activation of methylene C–H bonds to form C–C bonds.
Scheme 5
Scheme 5. Modification of complex molecules derived from natural products (see ESI for experimental details).
Fig. 1
Fig. 1. A (left), Crystal structure of compound 3kg; B (right), crystal structure of palladation intermediate 6 (see ESI for detailed date of the crystals).
Scheme 6
Scheme 6. Hydrogenation of 3aa to generate 3aa-H.
Scheme 7
Scheme 7. Preparation of the palladation intermediate and its reaction with 2d.
Scheme 8
Scheme 8. A plausible mechanism.
See this image and copyright information in PMC

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