Palladium-catalyzed C-H alkylation reaction with alkylboronic acids has successfully been developed using a removable pyridyldiisopropylsilyl directing group. The amino acid played a crucial role as a ligand in the reaction. The alkylation protocol is also applicable to the coupling of C(sp(3))-H bonds with alkylboronic acids.
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http://dx.doi.org/10.1039/c6ob00674d | DOI Listing |
Chemistry
December 2024
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, P. R. China.
Nickel/photoredox dual catalyzed cross-coupling of aryl halides with alkylboron compounds is one of the effective methodologies for the construction of C(sp)-C(sp) bonds. Although elegant results have been achieved by using alkyl trifluoroborates as alkyl radical precursors, the generation of alkyl radicals from readily available alkyl boronic esters is still limited due to their high oxidation potential. We disclosed here that activation of alkyl boronic esters by MeOLi is highly efficient for the generation of alkyl radicals under photocatalysis conditions.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Applied Chemistry for Environment, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 minami-Osawa, Hachioji 192-0397, Tokyo, Japan.
Chem Sci
November 2024
Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica "Enrique Moles", Instituto de Investigación Sanitaria del Principado de Asturias (ISPA), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Oviedo C/ Julián Clavería 8 33006 Oviedo Spain
The reactions of cyclic α,β-unsaturated -tosylhydrazones and alkylboronic acids promoted by 370-390 nm light in the presence of a base give rise to allylic boronic acids that can be trapped as the corresponding pinacolboronates by treatment with pinacol. This reaction features wide scope regarding both coupling partners and functional group tolerance, allowing for the incorporation of a variety of natural product-derived fragments. The allylic boronic acids can be also reacted in a one-pot process with aldehydes, to produce homoallylic alcohols with very high diastereoselectivity.
View Article and Find Full Text PDFOrg Lett
December 2024
Inner Mongolia Key Laboratory of Fine Organic Synthesis, College of Chemistry and Chemical Engineering, Inner Mongolia University (South Campus), 24 Zhaojun Road, Hohhot 010030, China.
Novel monophosphine ligands and with a C-P ring were designed and synthesized for the efficient Pd-catalyzed C(sp)-C(sp) Suzuki coupling. With 0.5 mol % Pddba and 2 mol % , aryl halides coupled with alkylboronic acids to give the products in up to 99% yield.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
National Institute of Biological Sciences, 7 Science Park Road, Zhongguancun Life Science Park, Beijing 102206, China.
Asymmetric decarboxylative cross-couplings of carboxylic acids are powerful methods for synthesizing chiral building blocks essential in medicinal chemistry and material science. Despite their potential, creating versatile chiral alkylboron derivatives through asymmetric decarboxylative C(sp)-C(sp) cross-coupling from readily available primary aliphatic acids and mild organometallic reagents remains challenging. In this study, we present a visible light-induced Ni-catalyzed enantioconvergent C(sp)-C(sp) cross-coupling of unactivated primary aliphatic acid NHPI esters with -borazirconocene alkanes, producing a diverse array of valuable chiral alkylboron building blocks.
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