Alkyl bromides bearing various functional groups are smoothly converted to functionalized alkylzinc reagents by the direct insertion of magnesium in the presence of LiCl and ZnCl(2).
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http://dx.doi.org/10.1039/c001845g | DOI Listing |
Nat Commun
October 2023
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology 130 Meilong Road, Shanghai, China.
Transition metal-catalyzed carbonylative reaction with CO gas are among the central task in organic synthesis, enabling the construction of highly valuable carbonyl compound. Here, we show an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence of allene and alkylzinc reagent with 1 atm of CO under mild conditions. This protocol is featured by broad functional group tolerance with high reaction selectivity, providing a rapid and convenient synthetic method for the construction of diverse fully substituted benzotropone derivatives.
View Article and Find Full Text PDFACS Catal
September 2023
Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA 53706.
Reactions that cleave C-C bonds and enable functionalization at both carbon sites are powerful strategic tools in synthetic chemistry. Stereodefined cyclopropyl ketones have become readily available and would be an ideal source of 3-carbon fragments, but general approaches to net C-C activation / difunctionalization are unknown. Herein we demonstrate the cross-coupling of cyclopropyl ketones with organozinc reagents and chlorotrimethylsilane to form 1,3-difunctionalized, ring-opened products.
View Article and Find Full Text PDFChem Sci
August 2023
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University Suzhou 215123 China
The construction of Csp-Csp bonds through Negishi-type reactions using alkylzinc reagents as the pronucleophiles is of great importance for the synthesis of pharmaceuticals and agrochemicals. However, the use of air and moisture sensitive solutions of conventional alkylzinc halides, which show unsatisfying reactivity and limitation of generality in twofold Csp-Csp cross-couplings, still represents drawbacks. We herein report the first preparation of solid and salt-stabilized alkylzinc pivalates by OPiv-coordination, which exhibit enhanced stability and a distinct advantage of reacting well in cobalt-catalyzed difluoroalkylation-alkylation of dienoates, thus achieving the modular and site-selective installation of CF- and Csp-groups across double bonds in a stereoretentive manifold.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2023
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.
The selective transition-metal catalyzed C-F bond functionalization of inexpensive industrial fluorochemicals represents one of the most attractive approaches to valuable fluorinated compounds. However, the selective C(sp )-F bond carbofunctionalization of refrigerant hydrofluoroolefins (HFOs) remains challenging. Here, we report a nickel-catalyzed selective C(sp )-F bond alkylation of HFO-1234yf with alkylzinc reagents.
View Article and Find Full Text PDFOrg Lett
January 2022
Key Laboratory of Biocatalysis & Chiral Drug Synthesis of Guizhou Province, Generic Drug Research Center of Guizhou Province, Zunyi Medical University, Zunyi, Guizhou 563000, China.
Unnatural α-amino acids are important synthetic targets in the field of peptide science. Herein we report an efficient, versatile, and straightforward strategy for the synthesis of homophenylalanine derivatives via the nickel-catalyzed Csp-Csp cross-coupling of (fluoro)benzyl bromides/chlorides with natural α-amino-acid-derived alkylzinc reagents. The current protocol features the advantages of a low-cost nickel catalyst system, synthetic convenience, and the tolerance of rich functionality and stereochemistry.
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