A C(sp)-C(sp) cross coupling approach based on an iridium-photocatalytic radical process has been developed enabling the synthesis of various α-alkylated aldehydes from easily available/synthesized alkyl bromides and trialkyl amines under mild photocatalytic conditions. The synthesized aldehydes are also explored as a functional handle for various useful products such as carboxylic acid, alcohol and N-heterocycle synthesis.
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http://dx.doi.org/10.1039/d4cc01043d | DOI Listing |
J Am Chem Soc
January 2025
Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education), Hubei Key Lab on Organic and Polymeric OptoElectronic Materials, College of Chemistry and Molecular Sciences, and TaiKang Center for Life and Medical Sciences, Wuhan University, Wuhan 430072, China.
A modular platform technology for the synthesis of α-aryl carbonyl derivatives via Borono-Catellani-type secondary alkylation of arenes is presented. This practical method features a broad substrate scope regarding aryl boronic acid catechol esters, secondary alkyl bromides, and diversified terminating reagents (e.g.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
This work introduces a novel Mn(I)-catalyzed enantioselective alkylation methodology that efficiently produces a wide array of P-chiral phosphines with outstanding yields and enantioselectivities. Notably, the exceptional reactivity of Mn(I) complexes in these reactions is demonstrated by their effective catalysis with both typically reactive alkyl iodides and bromides, as well as with less reactive alkyl chlorides. This approach broadens the accessibility to various P-chiral phosphines and simplifies the synthesis of chiral tridentate pincer phosphines to a concise 1-2 step process, contrary to conventional, labor-intensive multistep procedures.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi, 330031, China.
We present a highly efficient and versatile nickel-catalyzed protocol for the reductive cross-coupling of unactivated CFH-substituted electrophiles with a wide variety of aryl and alkenyl halides. This novel approach offers high catalytic reactivity and broad functional group compatibility, enabling late-stage fluoroalkylation of drug molecules.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Department of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang 414006, China.
1,4-Dibenzodiazepines, an important component of nitrogen-containing heterocycles, are widely present in drugs. Herein, we developed a photochemical radical cascade cyclization reaction of isocyanides with α-carbonyl bromides under mild conditions. A sequence of 11-alkyl-substituted 1,4-dibenzodiazepines were produced in 53%-85% yields, demonstrating excellent tolerance towards various functional groups.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, University of Wisconsin─Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.
Aryl triflates make up a class of aryl electrophiles that are available in a single step from the corresponding phenol. Despite the known reactivity of nickel complexes for aryl C-O bond activation of phenol derivatives, nickel-catalyzed cross-electrophile coupling using aryl triflates has proven challenging. Herein, we report a method to form C(sp)-C(sp) bonds by coupling aryl triflates with alkyl bromides and chlorides using phenanthroline (phen) or pyridine-2,6-bis(-cyanocarboxamidine) (PyBCam)-ligated nickel catalysts.
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