Visible-light photocatalysis has evolved as a powerful technique to enable controllable radical reactions. Exploring unique photocatalytic mode for obtaining new chemoselectivity and product diversity is of great significance. Herein, we present a photo-induced chemoselective 1,2-diheteroarylation of unactivated alkenes utilizing halopyridines and quinolines. The ring-fused azaarenes serve as not only substrate, but also potential precursors for halogen-atom abstraction for pyridyl radical generation in this photocatalysis. As a complement to metal catalysis, this photo-induced radical process with mild and redox neutral conditions assembles two different heteroaryl groups into alkenes regioselectively and contribute to broad substrates scope. The obtained products containing aza-arene units permit various further diversifications, demonstrating the synthetic utility of this protocol. We anticipate that this protocol will trigger the further advancement of photo-induced alkyl/aryl halides activation.
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http://dx.doi.org/10.1038/s41467-024-50460-4 | DOI Listing |
J Org Chem
December 2024
Department of Chemistry, National Institute of Technology, Tiruchirappalli 620015, Tamilnadu, India.
Sodium salt of aryl sulfinic acid reacts with enynone in a different manner, yielding α-furyl sulfone and stereodefined vinyl sulfone in toluene and EtOH respectively in the presence of ZnCl. The salient features of this protocol include chemoselectivity, broad substrate scope, high efficiency, high yield, and easy purification. The synthetic utilities of the products are demonstrated by cycloaddition and cis-trans photoisomerization reactions.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry and Center for Emerging Material and Advanced Devices, National Taiwan University, Taipei 106319, Taiwan (R.O.C.).
Reactive carbonyl species (RCS) are important biomarkers of oxidative stress-related diseases because of their highly reactive electrophilic nature. Despite their potential as triggers for prodrug activation, selective labeling approaches for RCS remain limited. Here, we utilized triphenylphosphonium groups to chemoselectively capture RCS via an aqueous Wittig reaction, forming α,β-unsaturated carbonyls that enable further functionalization.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Chemistry, Indian Institute of Science Education and Research (IISER)-Pune, Dr. Homi Bhabha Road, Pashan, Pune, Maharashtra 411008, India.
A Pd (II)-catalyzed direct C3-(sp)-H alkenylation of heteroarenes using benzothiazole as a directing group was successfully achieved. A wide range of 2--alkylpyrroles undergo an oxidative coupling with a variety of acrylates to furnish highly regio- and chemoselective E-alkenylation products at the C3 position. An important intermediate complex has been isolated and characterized so as to have an insight into the mechanism.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, United States.
The synthetic utility of tetrabenzyl pyrophosphate for achieving chemoselective phosphorylation of phenols, as well as primary, secondary, and tertiary alcohols, is reported here. Additionally, we introduce a rapid, mild, and chemoselective debenzylation procedure, enabling access to phosphates in the presence of redox sensitive groups. Finally, stoichiometrically controlled monodebenzylation provides a versatile platform for late-stage divergent synthesis of phosphodiester and phosphoramidate chemical libraries.
View Article and Find Full Text PDFOrg Lett
December 2024
State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China.
A visible light-driven, intermolecular interrupted Barton reaction has been developed for radical-relay sulfonyloximation of alkenes with alkyl nitrites, using DABSO as a trapping reagent. This method overcomes the challenges of competing normal Barton reactions and polarity mismatches by rapidly and irreversibly capturing alkyl radicals, preventing unwanted side reactions. The resulting polarity-reversed sulfonyl radicals undergo highly selective addition to alkenes, yielding α-alkylsulfonyl ketoximes tethered to hydroxyl or ketone groups.
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