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Oxidative Alkane C-H Alkoxycarbonylation

Oxidative Alkane C-H Alkoxycarbonylation

Chemistry 22(41): 14484-8

Directly utilizing a chemical feedstock to construct valuable compounds is an attractive prospect in organic synthesis. In particular, the combination of C(sp(3) )-H activation and oxidative carbonylation involving alkanes and CO gas is a promising and efficient method to synthesize carbonyl derivatives. However, due to the high C-H bond dissociation energy and low polarity of unactivated alkanes, the carbonylation of unactivated C(sp(3) )-H bonds still remains a great challenge. In this work, we introduce a palladium-catalyzed radical oxidative alkoxycarbonylation of alkanes to prepare numerous alkyl carboxylates. Various alkanes and alcohols were compatible, generating the desired products in up to 94‚ÄČ% yield. Remarkably, ethane, a constituent of natural gas, could be employed as a substrate under the standard reaction conditions. Preliminary mechanistic studies revealed a probable palladium-catalyzed radical process.

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Accession: 058488374

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PMID: 27308821

DOI: 10.1002/chem.201602791

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