[reaction: see text] Oxygen-promoted Pd(II) catalysis facilitated the synthesis of conjugated dienes by cross-coupling of alkenylboronic compounds and various olefins including highly substituted alkenes and cyclohexenone. Under mild conditions, these versatile reactions were efficient and highly stereoselective.
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http://dx.doi.org/10.1021/ol0483192 | DOI Listing |
Angew Chem Int Ed Engl
December 2022
Institute of Next Generation Matter Transformation, College of Material Sciences Engineering at Huaqiao University, 668 Jimei Boulevard, Xiamen, Fujian, 361021, China.
Transition-metal-catalyzed Suzuki-Miyaura coupling has significantly advanced C-C bond formation and has been well recognized in organic synthesis, pharmaceuticals, materials science and other fields. In this rapid development, cross coupling without transition metal catalyst is a big challenge in this field, and using widely existing tertiary amines as electrophiles to directly couple with boronic acids has great hurdles yet significant application prospects. Herein, we report an efficient and general deaminative arylation and alkenylation of tertiary amines (propargyl amines, allyl amines and 1H-indol-3-yl methane amines) with ary and alkenylboronic acids enabled by difluorocarbene under transition-metal-free conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2023
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
The site-selective palladium-catalyzed three-component coupling of unactivated alkenyl carbonyl compounds, aryl- or alkenylboronic acids, and N-fluorobenzenesulfonimide is described herein. Tuning of the steric environment on the bidentate directing auxiliary enhances regioselectivity and facilitates challenging C(sp )-F reductive elimination from a Pd intermediate to afford 1,2-carbofluorination products in moderate to good yields.
View Article and Find Full Text PDFChem Commun (Camb)
April 2022
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, China.
The TMSCF-derived CuCFCF species has been successfully applied in pentafluoroethylation of organoboronates and terminal alkynes. By using 1,10-phenanthroline as a ligand, a broad range of (hetero)arylboronates and alkenylboronates were smoothly pentafluoroethylated under aerobic conditions. Furthermore, terminal alkynes can undergo aerobic cross-coupling with the TMSCF-derived CuCFCF species in the absence of additional ligands.
View Article and Find Full Text PDFJ Am Chem Soc
April 2022
Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Southern University of Science and Technology, Shenzhen 518055, China.
The enantioconvergent radical C(sp)-C(sp) cross-coupling of alkyl halides with alkenylboronate esters is an appealing tool in the assembly of synthetically valuable enantioenriched alkenes owing to the ready availability, low toxicity, and air/moisture stability of alkenylboronate esters. Here, we report a copper/chiral N,N,N-ligand catalytic system for the enantioconvergent cross-coupling of benzyl/propargyl halides with alkenylboronate esters (>80 examples) with good functional group tolerance. The key to the success is the rational design of hemilabile N,N,N-ligands by mounting steric hindrance at the ortho position of one coordinating quinoline ring.
View Article and Find Full Text PDFDalton Trans
January 2022
Research Institute for Interdisciplinary Science, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan.
The Suzuki-Miyaura reaction (the cross-coupling reaction of boronic acids with organic halides catalysed by Pd complexes) has been recognised as a useful synthetic organic reaction that forms a C(sp)-C(sp) bond. The catalytic cycle of the reaction involves the transmetalation of aryl- and alkenylboronic acids with Pd(II) complexes. It migrates the aryl and alkenyl groups of boronic acid to Pd and produces a Pd-C bond.
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