Disclosed herein is the first example of radical-mediated remote migration of quinoxalinones. The quinoxalinonyl-functionalization of alkenes employs the quinoxalinone-substituted tertiary bishomoallylic alcohols as substrates, proceeds through intramolecular 1,4-quinoxalinone migration, and gives rise to complex γ-quinoxalinone-substituted aliphatic ketones. A set of external radicals is compatible with this method. The protocol features broad tolerance of functional groups, good adaptability to various external radicals and high product diversity, and opens a new door for the synthesis of quinoxalinone derivatives.
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http://dx.doi.org/10.1039/d2cc06887g | DOI Listing |
Chem Commun (Camb)
December 2024
Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study, and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
The application of rearrangement reactions offers opportunities for the efficient construction of complex molecules that are challenging to obtain through conventional synthetic methods. However, the development of radical-mediated rearrangements has lagged far behind that of ionic-type rearrangements, due to the uncontrollability of radical species. Along with the recent renaissance in radical chemistry, radical-mediated functional group migration (FGM) reactions provide a versatile platform for the selective incorporation of functional groups across different molecular distances, enabling the construction of intricate molecular architectures.
View Article and Find Full Text PDFMolecules
July 2024
Department of Chemistry, University of Massachusetts Boston, 100 Morrissey Boulevard, Boston, MA 02125, USA.
Synthetic radicals have intrinsic power for cascading and multifunctional reactions to construct diverse molecular scaffolds. In the previous review series, we covered 1,2-difunctionalizations, remote 1,3-, 1,4-, 1,5-, 1,6-, and 1,7-difunctionalizations, addition followed by cyclization reactions, and cycloaddition-initiated difunctionalizations. Presented in this paper are radical addition-initiated trifunctionalization reactions of alkenes, alkynes, and their derivatives.
View Article and Find Full Text PDFOrg Lett
May 2024
Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, China West Normal University, Nanchong, Sichuan 637002, People's Republic of China.
We report a novel organic photoredox catalysis to achieve unprecedented γ-(hetero)aryl/alkenyl-δ-silyl aliphatic amines via silyl-mediated distal (hetero)aryl/alkenyl migration of aromatic/alkenyl amines bearing unactivated alkenes with hydrosilanes. This protocol features mild and metal-free reaction conditions, high atom economy, excellent selectivity, and functional group compatibility. Mechanistic studies suggest that silylation and (hetero)aryl/alkenylation involve photoredox hydrogen atom transfer catalysis and subsequent 1,4-migration of a remote (hetero)aryl/alkenyl group from nitrogen to carbon.
View Article and Find Full Text PDFChem Sci
May 2024
State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University Changsha 410082 China
Site selective functionalization of inert remote C(sp)-H bonds to increase molecular complexity offers vital potential for chemical synthesis and new drug development, thus it has been attracting ongoing research interest. In particular, typical β-C(sp)-H arylation methods using chelation-assisted metal catalysis or metal-catalyzed oxidative/photochemical generated allyl C(sp)-H bond processes have been well developed. However, radical-mediated direct β-C(sp)-H arylation of carbonyls remains elusive.
View Article and Find Full Text PDFChem Commun (Camb)
April 2024
College of Chemistry and Chemical Engineering, Jishou University, Jishou 416000, China.
A radical 1,4-aryl migration enabling a cross-electrophile coupling reaction toward remote alkylation of -benzyl alanine has been developed. In this strategy, with the occurrence of a radical-mediated Turce-Smiles rearrangement, key α-aminoalkyl radicals are generated. The as-formed α-aminoalkyl radical serves as a robust coupling partner for cross-electrophilic coupling with vinyl triflates, affording a series of olefin-tethered amino acid motifs.
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