A direct room-temperature Ni-catalyzed cross-coupling of aminoalkylzinc halides, readily available from the corresponding aminoalkyl chlorides via Grignard reagents, with aryl and hetaryl electrophiles, allows a convenient one-step preparation of aminoalkyl (het)arenes, bearing a basic tertiary nitrogen in the side chain, including piperidine and tropane derivatives. Such aminoalkylarene scaffolds are widely present in various biologically active molecules.
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http://dx.doi.org/10.1021/ol702499h | DOI Listing |
J Am Chem Soc
September 2024
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing 100084, China.
Halogen atom transfer (XAT) is a versatile method for generating carbon radicals. Recent interest has focused on α-aminoalkyl radicals as potential XAT reagents, previously reported to exhibit reactivity comparable to tin radicals. Utilizing an advanced time-resolved EPR technique, the XAT reactions between α-aminoalkyl radicals and organic halides were examined, allowing direct observation of the process through EPR spectroscopy and analysis of radical kinetics.
View Article and Find Full Text PDFOrg Lett
July 2024
Flow Chemistry Group, van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, 1098 XH Amsterdam, The Netherlands.
Light-mediated Halogen-Atom Transfer (XAT) has become a significant methodology in contemporary synthesis. Unlike α-aminoalkyl and silyl radicals, ligated boryl radicals (LBRs) have not been extensively explored as halogen atom abstractors. In this study, we introduce NHC-ligated boranes as optimal radical chain carriers for the intermolecular reductive radical hydroalkylation and hydroarylation of electron-deficient olefins by using direct UV-A light irradiation.
View Article and Find Full Text PDFOrg Lett
June 2024
Henan University of Chinese Medicine, Zhengzhou 450046, China.
The hybrid nature of Pd(I)-alkyl radical species has enabled a wide array of radical-based transformations. However, in this transformation, the secondary Pd(I)-alkyl radical species are prone to recombining into Pd(II)-alkyl species to give Heck-type products via β-H loss. Herein, we report a visible-light-induced, three-component Pd-catalyzed 1,2-aminoalkylation of alkenes with readily available alkyl halides and amines to construct C-C and C-N bonds simultaneously.
View Article and Find Full Text PDFChem Commun (Camb)
January 2024
Professor of Organic Chemistry I, Faculty of Chemistry and Food Chemistry, TU Dresden, Bergstrasse 66, Dresden DE-01069, Germany.
Benzylic amine derivatives are ubiquitous structural motifs in organic chemistry. Herein we report a direct synthesis of these compounds a direct desulfonylative -arylation of -tosyl hydroxamates. The applicability of this Ru-catalyzed aminoalkylation is being exemplified by a set of late-stage functionalizations of natural products.
View Article and Find Full Text PDFChem Sci
December 2023
Graduate School of Pharmaceutical Sciences, Kyoto University Sakyo Kyoto 606-8501 Japan
1,2-Aminoalcohols are common motifs found in a wide range of natural products and pharmaceutical compounds. Here we report a photocatalytic method for the direct conversion of readily available aliphatic alcohols into synthetically valuable 1,2-aminoalcohols. A dual catalytic system consisting of an acridinium photoredox catalyst and a cationic hydrogen-atom transfer (HAT) catalyst based on 1,4-diazabicyclo[2.
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