Nickel HAS it: A Ni(cod)2/dppp catalyst system promotes the direct alkylation of electron-rich heterocycles with α-bromo carbonyl compounds and involves an alkyl radical intermediate (see scheme; cod = 1,5-cyclooctadiene, dppp = 1,3-bis(diphenylphosphino)propane). This homolytic radical aromatic substitution (HAS)-type reaction enables the C3-selective direct functionalization of 2-pyridones.
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http://dx.doi.org/10.1002/chem.201301350 | DOI Listing |
Leukemia
January 2025
Department of Medicine III, LMU University Hospital, LMU Munich, Munich, Germany.
Refractory disease and relapse are major challenges in acute myeloid leukemia (AML) therapy attributed to survival of leukemic stem cells (LSC). To target LSCs, antibody-drug conjugates (ADCs) provide an elegant solution, combining the specificity of antibodies with highly potent payloads. We aimed to investigate if FLT3-20D9h3-ADCs delivering either the DNA-alkylator duocarmycin (DUBA) or the microtubule-toxin monomethyl auristatin F (MMAF) can eradicate quiescent LSCs.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Key Laboratory of Green Chemical Process of Ministry of Education, Hubei Key Laboratory of Novel Chemical Reactor and Green Chemical Technology, School of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430073, P.R. China.
Electrochemical oxidative cross-dehydrogenative-coupling (CDC) is an ideal strategy to conduct the C3-alkoxylation of imidazo[1,2-]pyridine, but it remains a challenge owing to limitation imposed by the use of alkyl alcohols and carboxylic acids. Herein, we report a mild and efficient 2-electrode constant-potential electrolysis of imidazo[1,2-]pyridine with hexafluoroisopropanol (HFIP) to produce various imidazo[1,2-]pyridine HFIP ethers. Mechanistic studies indicated that the electrooxidation reaction might involve radical coupling and ionic reaction.
View Article and Find Full Text PDFChem Sci
January 2025
College of Chemistry and Chemical Engineering, Key (Guangdong-Hong Kong Joint) Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University Shantou 515063 P. R. China
In the past few years, the direct activation of organohalides by ligated boryl radicals has emerged as a potential synthetic tool for cross-coupling reactions. In most existing methods, ligated boryl radicals are accessed from NHC-boranes or amine-boranes. In this work, we report a new photocatalytic platform by modular assembly of readily available amines and diboron esters to access a library of ligated boryl radicals for reaction screening, thus enabling the cross-coupling of organohalides and alkenes including both activated and unactivated ones for C(sp)-C(sp) bond formation by using the assembly of DABCO A1 and BNepB1.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shanghai Jiao Tong University, Frontiers Science Center for Transformative Molecules, CHINA.
A photoelectrocatalytic method is presented that achieves direct decarboxylative C(sp3)-P coupling, providing a modular route to alkylphosphinates and alkylphosphonates from readily available carboxylic acids. The success of this reaction hinges on the synergistic combination of electrochemical anodic oxidation and photocatalytic ligand to metal charge transfer (LMCT) decarboxylation. By employing P(III) reagents as limiting reagents, our approach enables efficient alkyl modification of medicinally important nucleosides and complex molecules derived phosphonites, which were challenging to access by existing methods.
View Article and Find Full Text PDFNat Commun
January 2025
School of Environmental and Chemical Engineering, Wuyi University, Jiangmen, PR China.
Developing efficient strategies for the deoxygenative functionalization of carbonyl compounds is crucial for enhancing the effective utilization of biomass and the upgrading of chemical feedstocks. In this study, we present an elegant cathodic reduction strategy that enables a tandem alkylation/dearomatization reaction between quinoline derivatives and aryl aldehydes/ketones in a one-pot process. Our approach can be executed via two distinct paths: the aluminum (Al)-facilitated spin-center shift (SCS) path and the Al-facilitated direct deoxygenation path.
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