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Abstract Dehydrogenation chemistry has long been established as a fundamental aspect of organic synthesis, commonly encountered in carbonyl compounds. Transition metal catalysis revolutionized it, with strategies like transfer-dehydrogenation, single electron transfer and C–H activation. These approaches, extended to multiple dehydrogenations, can lead to aromatization. Dehydrogenative transformations of aliphatic carboxylic acids pose challenges, yet engineered ligands and metal catalysis can initiate dehydrogenation via C–H activation, though outcomes vary based on substrate structures. Herein, we have developed a catalytic system enabling cyclohexane carboxylic acids to undergo multifold C–H activation to furnish olefinated arenes, bypassing lactone formation. This showcases unique reactivity in aliphatic carboxylic acids, involving tandem dehydrogenation-olefination-decarboxylation-aromatization sequences, validated by control experiments and key intermediate isolation. For cyclopentane carboxylic acids, reluctant to aromatization, the catalytic system facilitates controlled dehydrogenation, providing difunctionalized cyclopentenes through tandem dehydrogenation-olefination-decarboxylation-allylic acyloxylation sequences. This transformation expands carboxylic acids into diverse molecular entities with wide applications, underscoring its importance.
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Predominant intermolecular decarbonylative thioetherification of carboxylic acids using nickel precatalysts
We report a general method for direct decarbonylative thioetherification of carboxylic acids using air- and moisture-stable nickel precatalysts. In this approach, ubiquitous carboxylic acids are directly used as aryl electrophiles and common thiols serve as sulfide donors.
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- Award ID(s):
- 1650766
- PAR ID:
- 10519503
- Publisher / Repository:
- RSC
- Date Published:
- Journal Name:
- Organic Chemistry Frontiers
- Volume:
- 10
- Issue:
- 17
- ISSN:
- 2052-4129
- Page Range / eLocation ID:
- 4275 to 4281
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D3QO00744H
