98%
921
2 minutes
20
Unlike many other state-of-the-art transition-metal-catalyzed allylic substitutions, cobalt-catalyzed allylic substitution has received much less attention from synthetic chemists for a long time despite the fact that cobalt is an earth-abundant, low-cost and thus much more sustainable option as either a reagent or a catalyst in organic synthesis. Recently, there has been an upsurge in the use of cobalt catalysis in allylic functionalization reactions, including allylic substitution, nucleophilic allylation, and Heck-type allylic functionalization, to construct synthetically significant building blocks featuring a double bond available for diverse downstream synthetic manipulations. This review highlights the current development of cobalt catalysis in allylic functionalization with an in-depth discussion of the reaction scope and mechanistic insights.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/d0ob01581d | DOI Listing |
J Org Chem
September 2025
Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116, PR China.
A convenient protocol for the synthesis of selenated benzoxepine derivatives via iron(III)-catalyzed 7-endo-trig cyclization has been first established via reaction of 1,7-diene containing nonactivated allyl and dialkyl diselenides under room temperature and air conditions. Research has shown that different dialkyl diselenides could react with a wide range of 1,7-diene to achieve seven-membered products in good to excellent yields. Furthermore, this synthesis was directed to obtain the desired target products, indicating that this approach has an excellent chemical selectivity.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Department of Chemistry and Biochemistry, The University of Texas at Dallas, Richardson, Texas 75080-3021, United States.
The direct transformation of C-H bonds into C-C bonds via cross-dehydrogenative coupling (CDC) represents a powerful strategy in synthetic chemistry, enabling streamlined bond construction without the need for prefunctionalized substrates. While traditional CDC approaches rely on polar mechanisms and preactivation of one of the C-H partners, recent advances have introduced radical-based strategies that employ a hydrogen atom transfer (HAT) approach to access carbon-centered radicals from unactivated substrates. Herein, we report a nickel-catalyzed CDC reaction between aldehydes and alkenes for the synthesis of skipped enones, leveraging aryl radicals as intermolecular HAT agents.
View Article and Find Full Text PDFOrg Lett
September 2025
School of Chemical Sciences, National Institute of Science Education and Research (NISER), An OCC of Homi Bhabha National Institute, Bhubaneswar 752050, India.
A manganese(II)-catalyzed anti-Markovnikov addition of diarylphosphine oxides to primary and secondary allylic alcohols has been developed, which delivered synthetically valuable γ-hydroxy phosphine oxides. The reaction proceeds under mild, base-assisted conditions with a broad substrate scope and excellent functional group tolerance. Mechanistic studies indicate the involvement of a homogeneous catalytic system and a radical pathway.
View Article and Find Full Text PDFJ Org Chem
September 2025
State Key Laboratory of Southwestern Chinese Medicine Resources, School of Pharmacy, Chengdu University of Traditional Chinese Medicine, Chengdu 611137, China.
Radical-radical cross-coupling offers an efficient strategy for constructing C-S bonds, yet existing methods typically rely on stoichiometric oxidants or metal catalysts. The lack of sustainable approaches for C(sp)-H sulfenylation at the C9 position of xanthene derivatives limits their functionalization. Herein, we developed an electrochemical method enabling direct C(sp)-H sulfenylation/selenylation of oxa/thia/aza-xanthenes under metal- and chemical-oxidant-free conditions.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
School of Chemistry and Material Engineering, Anhui Provincial Key Laboratory of Green Carbon Chemistry, Engineering Research Center of Biomass Conversion and Pollution Prevention of Anhui Educational Institutions, Biomass-derived Functional Oligosaccharides Engineering Technology Research Center of
A solvent- and catalyst-free protocol for the selective reductive deoxygenation of α,β-unsaturated ketones with pinacolborane (HBpin) has been developed. -OH/NH groups efficiently direct the transformation, affording 2-allylphenols and 2-allylanilines under mild conditions with excellent chemo- and regioselectivity. Mechanistic studies indicate a boron-assisted hydride transfer and carbocation pathway.
View Article and Find Full Text PDF