We report the development of ureas as sterically undemanding pro-ligands for Pd catalysis. -Arylureas outperform phosphine ligands for the Pd-catalyzed heteroannulation of -tosyl--bromoanilines and 1,3-dienes, engaging diverse coupling partners for the preparation of 2-subsituted indolines, including sterically demanding substrates that have not previously been tolerated. Experimental and computational studies on model Pd-urea and Pd-ureate complexes are consistent with monodentate binding through the nonsubstituted nitrogen, which is uncommon for metal-ureate complexes.
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http://dx.doi.org/10.1021/jacs.2c01019 | DOI Listing |
J Am Chem Soc
February 2023
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
Aromatic polycyclic systems have been extensively utilized as structural subunits for the preparation of various functional molecules. Currently, aromatics-based polycyclic systems are predominantly generated from the extension of two-dimensional (2D) aromatic rings. In contrast, polycyclic compounds based on the extension of three-dimensional (3D) aromatics such as boron clusters are less studied.
View Article and Find Full Text PDFOrg Lett
April 2022
EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife KY16 9ST, United Kingdom.
A Pd-catalyzed heteroannulation approach for the synthesis of C2 borylated indoles is reported. The process allows access to highly functionalized 2-borylated indole scaffolds with complete control of regioselectivity. The utility of the process is demonstrated in the synthesis of borylated sulfa drugs and in the concise synthesis of the alkaloid Goniomitine.
View Article and Find Full Text PDFJ Am Chem Soc
April 2022
Department of Chemistry, University of Rochester, Rochester, New York 14627, United States.
We report the development of ureas as sterically undemanding pro-ligands for Pd catalysis. -Arylureas outperform phosphine ligands for the Pd-catalyzed heteroannulation of -tosyl--bromoanilines and 1,3-dienes, engaging diverse coupling partners for the preparation of 2-subsituted indolines, including sterically demanding substrates that have not previously been tolerated. Experimental and computational studies on model Pd-urea and Pd-ureate complexes are consistent with monodentate binding through the nonsubstituted nitrogen, which is uncommon for metal-ureate complexes.
View Article and Find Full Text PDFJ Org Chem
April 2022
Department of Pure Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow G1 1XL, U.K.
A modular approach to prepare tri- and tetracyclic carbazoles by a sequential [3 + 2]heteroannulation is described. First, optimization of Pd-catalyzed Buchwald-Hartwig amination followed by C/N-arylation in a one-pot process is established. Second, mechanistic analyses identified the origins of chemo- and regioselective sequential control of both bond-forming steps.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2016
Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne (Switzerland) http://lspn.epfl.ch.
A divergent total synthesis of three structurally distinct natural products from imine 9 was accomplished through an approach featuring: 1) a Pd-catalyzed decarboxylative cross-coupling, and 2) heteroannulation of 9 with bromoacetaldehyde and oxalyl chloride to give tetrahydroindolizine 6 and dioxopyrrole 7, respectively. The former was converted into (-)-rhazinilam, while the latter was converted into (-)-leucomidine B and (+)-leuconodine F. A substrate-directed highly diastereoselective reduction of a sterically unbiased double bond by using a homogeneous palladium catalyst was developed.
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