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. 2015 Aug 1;6(8):4610-4614.
doi: 10.1039/c5sc00519a. Epub 2015 May 19.

Oxalyl amide assisted palladium-catalyzed synthesis of pyrrolidones via carbonylation of γ-C(sp3)-H bonds of aliphatic amine substrates

Chao Wang  1 , Li Zhang  1 , Changpeng Chen  1 , Jian Han  1 , Yingming Yao  1 , Yingsheng Zhao  1
Affiliations

Oxalyl amide assisted palladium-catalyzed synthesis of pyrrolidones via carbonylation of γ-C(sp3)-H bonds of aliphatic amine substrates

Chao Wang et al. Chem Sci. .

Abstract

The first Pd-catalyzed regioselective γ-carbonylation of oxalyl amide protected aliphatic amines with carbon monoxide leading to synthesis of pyrrolidones has been developed. Both γ-methyl and cyclopropyl methylene C-H bonds are well activated to obtain the corresponding pyrrolidones in moderate to excellent yields. The role of 3-(trifluoromethyl)benzoic acid as an additive is critical as it helps in stabilizing the palladium intermediate formed during the catalytic cycle. The reaction scope is extended to benzylamine and allyl amine derivatives, thereby affording the corresponding products in good to excellent yields.

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Figures

Scheme 1
Scheme 1. Carbonylation of C(sp3)–H Bonds.
Scheme 2
Scheme 2. Carbonylation of allylamine reaction.
Scheme 3
Scheme 3. Scaling up and auxiliary removal.
See this image and copyright information in PMC

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