AgSbF6-controlled diastereodivergent hydroarylation reactions were developed. Unprecedented and remarkable switching of the E/Z-stereoselectivity could be obtained by adjusting the AgSbF6 loading.
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http://dx.doi.org/10.1039/c4cc03602f | DOI Listing |
J Org Chem
December 2024
School of Chemistry and Chemical Engineering, Hefei University of Technology, 193 Tunxi Road, Hefei 230009, China.
A Pd/C-catalyzed dehydrogenative [3 + 2] cycloaddition is described for the diastereoswitchable synthesis of hexahydropyrrolo[2,1-]isoquinolines by altering solvents. The reaction proceeds through a sequential Pd/C-catalyzed dehydrogenative formation of azomethine ylides from tetrahydroisoquinoline acetates and 1,3-dipolar cycloaddition with 2-nitroethenylbenzenes. This method displayed tunable diastereoselectivity, a broad substrate scope and good functional group compatibility.
View Article and Find Full Text PDFChem Soc Rev
December 2024
Department of Chemistry, Yonsei University, Seoul 03722, South Korea.
Catalytic asymmetric conjugate additions of carbon nucleophiles have emerged as a potent tool for constructing multi-stereogenic molecules with precise stereochemical control. This review explores the concept of diastereodivergence in such reactions, focusing on strategies to achieve selective access to diverse diastereomeric products upon carbon-carbon bond formation. Drawing from a rich array of examples, we delve into key approaches for controlling the stereochemical outcome of these transformations, including alteration of alkene geometry, fine-tuning of reaction parameters, synergistic catalysis, and isomerization of conjugate adducts.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Bhopal By-Pass Road, Bhopal, Madhya Pradesh 462066, India.
Herein, we disclose the first temperature-dependent diastereodivergent [4 + 3] annulation of ferrocene--tosylamides C-H activation with allenes by a Rh catalyst. At room temperature, Rh-catalyzed [4 + 3] annulation selectively offered a kinetically controlled diastereomer [>20:1 diastereomeric ratio (dr)], whereas at 60 °C, a thermodynamically controlled diastereomer was obtained exclusively with >20:1 dr.
View Article and Find Full Text PDFPrecis Chem
May 2024
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou 221116, China.
The catalytic asymmetric diastereodivergent synthesis of axially chiral 2-alkenylindoles was established via chiral phosphoric acid-catalyzed addition reactions of C3-unsubstituted 2-alkenylindoles with -hydroxybenzyl alcohols under different reaction conditions. Using this strategy, two series of 2-alkenylindoles bearing both axial and central chirality were synthesized in a diastereodivergent fashion with moderate to high yields and good stereoselectivities (up to 99% yield, 95:5 er, >95:5 dr). Moreover, theoretical calculations were performed on the key transition states leading to different stereoisomers, which provided an in-depth understanding of the origin of the observed stereoselectivity and diastereodivergence of the products under different reaction conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Institute of Microbial Chemistry (BIKAKEN), Tokyo, 3-14-23 Kamiosaki Shinagawa-ku, Tokyo, 141-0021, Japan.
Rocaglaol, a representative flavagline, has attracted significant attention because of its unique chemical structure and biological activities. This paper reports a mild and scalable copper-catalyzed enantioselective conjugate addition of benzofuran-3(2H)-ones to α,β-unsaturated thioamides. This method allows for the concise synthesis of all possible stereoisomers of a key intermediate of rocaglaol and its derivatives in a highly diastereo- and enantioselective manner using different chiral phosphine ligands.
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