The palladium-catalyzed Suzuki-Miyaura cross-couplings of nitroarenes and heteroarylboronate esters has been developed. A number of heterobiaryl compounds containing pyridine, pyrimidine, quinoline, furan, thiophene, and pyrazole were prepared using [Pd(cinnamyl)Cl]/2-aryl-5-(2,4,6-triisopropylphenyl)-2,3-imidazolylidene[1,5-]pyridines as the catalysts in good to excellent yields. The synthetic practicality of this approach is demonstrated through the synthesis of druglike molecules.
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http://dx.doi.org/10.1021/acs.orglett.2c02796 | DOI Listing |
J Am Chem Soc
October 2024
Hubei Research Center of Fundamental Science-Chemistry, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
Chiral tetrahydro-β-carbolines, as one of the most intriguing subtypes of indole alkaloids, have emerged as the privileged units in plenty of natural products and biologically active molecules with an impressive range of bioactive properties. However, the stereodivergent construction of these valuable skeletons containing multistereogenic centers from readily available starting materials remains very challenging, especially, in view of the introduction of an axial chirality. Herein, we developed an efficient method toward enantioenriched tetrahydro-β-carbolines with readily available tryptophan-derived aldimine esters and allylic carbonates under mild reaction conditions.
View Article and Find Full Text PDFNat Commun
August 2024
Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, China.
Atropisomeric biaryls bearing carbonyl groups have attracted increasing attention due to their prevalence in diverse bioactive molecules and crucial role as efficient organo-catalysts or ligands in asymmetric transformations. However, their preparation often involves tedious multiple steps, and the direct synthesis via asymmetric carbonylation has scarcely been investigated. Herein, we report an efficient palladium-catalyzed enantioconvergent aminocarbonylation of racemic heterobiaryl triflates with amines via dynamic kinetic asymmetric transformation (DyKAT).
View Article and Find Full Text PDFNat Commun
August 2024
Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education. State Key Laboratory of Green Pesticide, College of Chemistry, Central China Normal University, Wuhan, 430079, China.
The construction of atropisomers with 1,2-diaxes, while maintaining high enantiocontrol, presents a significant challenge due to the dynamic nature of steric hindrance at ortho-aryl substituents. Although various catalytic asymmetric methods have been developed for accessing axially chiral arylpyrroles, the synthesis of axially chiral arylpyrroles with 1,2-diaxes in a catalytic asymmetric manner has remained rare. Herein, the authors report the synthesis of diverse axially chiral arylpyrroles with 1,2-diaxes, and C-C and C-N axes through copper-catalysed asymmetirc [4 + 1] annulation of yne-allylic esters with arylamines via a remote stereocontrol strategy.
View Article and Find Full Text PDFOrg Lett
August 2024
Shanghai Key Laboratory of Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P. R. China.
There are only a few examples being reported for the simultaneous control of central chirality and axial chirality because it is more challenging. Herein, we report an iridium-catalyzed asymmetric hydroarylation of unactivated alkenes with heterobiaryls to simultaneously construct axial and central chirality. The reaction showed a broad substrate scope and delivered the products with satisfactory results.
View Article and Find Full Text PDFChem Sci
June 2024
Department of Pharmaceutical Engineering, State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology Dalian 116024 P. R. China
An unprecedented and straightforward route for the asymmetric construction of privileged atroposelective bridged (hetero)biaryl eight-membered scaffolds has been accomplished through chiral phosphoric acid catalyzed asymmetric intramolecular [3 + 2] cycloaddition of innovative (hetero)biaryl aldehydes with 3-aminooxindole hydrochlorides. A class of eight-membered bridged (hetero)biaryl lactones fused to spiro[pyrrolidine-oxindole] derivatives, possessing both chiral C-C/C-N axes and multiple contiguous stereocenters, were obtained in good yields with excellent enantioselectivities and diastereoselectivities in one step through this direct strategy. In addition, the good scalability and derivatization of the title compounds demonstrated their synthetic utility.
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