A three-component coupling strategy for 1,4-dicarbofunctionalization of 1,3-butadiene with C-H bearing substrates has been developed using photoinduced Pd catalysis, with aryl bromide serving as the hydrogen atom transfer (HAT) reagent. This photocatalytic coupling process achieves functionalized oxindole motifs in good yield and regioselectivity under mild reaction conditions. The versatility and synthetic utility of this method are demonstrated through the addition of a variety of C-H-bearing partners and various oxindole substrates to both substituted and unsubstituted butadiene.
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http://dx.doi.org/10.1021/acs.orglett.4c04410 | DOI Listing |
Org Lett
January 2025
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China.
A three-component coupling strategy for 1,4-dicarbofunctionalization of 1,3-butadiene with C-H bearing substrates has been developed using photoinduced Pd catalysis, with aryl bromide serving as the hydrogen atom transfer (HAT) reagent. This photocatalytic coupling process achieves functionalized oxindole motifs in good yield and regioselectivity under mild reaction conditions. The versatility and synthetic utility of this method are demonstrated through the addition of a variety of C-H-bearing partners and various oxindole substrates to both substituted and unsubstituted butadiene.
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October 2024
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China.
Herein, a photoinduced, Pd-catalyzed direct 1,2-carboamination of conjugated 1,3-dienes has been successfully achieved. Sequential regioselective C-C bond and enantioselective C-N bond formation allows rapid assembly of a wide range of value-added chiral allylic amines from readily available -hydroxyphthalimide (NHP) esters and 1,3-dienes under mild conditions. This developed protocol further demonstrates the versatility and potency of the photoexcited Pd catalytic system with a bifunctional reagent in the streamlined difunctionalization of C═C bonds.
View Article and Find Full Text PDFOrg Lett
October 2024
School of Chemistry and Chemical Engineering, Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Department Flexible Composite Materials Key Technology Center, Hefei University of Technology, Hefei 230009, China.
Here, we present a general method for the photoinduced Pd-catalyzed deoxygenative Heck reaction of vinyl arenes with -iodophenyl-thionocarbonate derived from alcohols. Mechanistic studies reveal that the deoxygenation involves a 5--trig cyclization and fragmentation process, with radical addition identified as the rate-determining step in this transformation. This one-pot procedure demonstrates excellent selectivity for less hindered hydroxyl groups in diols, facilitating late-stage functionalization of complex molecules and scalability to gram-scale synthesis.
View Article and Find Full Text PDFChem Commun (Camb)
October 2024
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China.
Herein, we report a photoinduced 1,7-hydrosulfonylation of allylic ethers and amides a sequential Pd-mediated 1,5-HAT process and Pd-catalyzed allylic nucleophilic attack of arylsulfonates. This rationally designed synthetic protocol allows for facile construction of a series of structurally novel allylic sulfonated scaffolds, and features mild conditions, cheap and readily available raw materials and functional group compatibility.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Department of Chemistry and Biochemistry, The University of Texas at Dallas, 800 West Campbell Road, Richardson, Texas, 75080-3021, United States.
Allylic sulfones are valuable motifs due to their medicinal and biological significance and their versatile chemical reactivities. While direct allylic C-H sulfonylation represents a straightforward and desirable approach, these methods are primarily restricted to terminal alkenes, leaving the engagement of the internal counterparts a formidable challenge. Herein we report a photocatalytic approach that accommodates both cyclic and acyclic internal alkenes with diverse substitution patterns and electronic properties.
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