An efficient synthetic protocol involving iron-catalyzed cross-coupling reactions between organolithium compounds and alkenyl iodides as key coupling partners was achieved. More than 30 examples were obtained with moderate to good yields and high stereospecificity. Gram-scale and synthetic applications of this procedure are recorded herein to demonstrate its feasibility and potential utilization.
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http://dx.doi.org/10.1021/acs.orglett.9b00394 | DOI Listing |
Chem Sci
November 2024
Stratingh Institute for Chemistry, University of Groningen Nijenborgh 3 9747 AG Groningen The Netherlands
Catalytic electrochemical asymmetric catalysis is emerging as a promising strategy for the synthesis of chiral compounds. Herein, we report an asymmetric electrochemical nickel-catalysed reductive conjugate addition of alkenyl bromides/aryl iodides to α,β-unsaturated ketones in an undivided cell, leading to addition products with high yields and excellent enantioselectivities (up to 96% yield and 96% ee).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, 200240, People's Republic of China.
Chemically modified oligonucleotides have garnered significant attention in medicinal chemistry, chemical biology, and synthetic biology due to their enhanced stability in vivo compared to naturally occurring oligonucleotides. However, current methods for synthesizing modified nucleosides, particularly at the C2'-position, are limited in terms of efficiency, modularity, and selectivity. Herein, we report a new approach for the synthesis of highly functionalized C2'-α-aryl/alkenyl nucleosides via an electrochemical nickel-catalyzed cross-coupling of 2'-bromo nucleosides with a variety of (hetero)aryl and alkenyl iodides.
View Article and Find Full Text PDFOrg Biomol Chem
November 2024
Department of Chemistry, School of Pharmacy, The Air Force Medical University, 169 Changle West Road, Xi'an 710032, P. R. China.
In this paper, chiral aryl iodides were used for the first time to catalyze the formation of C-O and C-N bonds of inactive olefins to obtain optically active aminolactone derivatives. The reaction is compatible with various substituted alkenyl carboxylic acid substrates. This method usually shows high activity and enantioselectivity, with a yield of up to 83% and an ee of up to 99%.
View Article and Find Full Text PDFSci Adv
November 2024
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
We present a versatile nickel-electrocatalytic deaminative cross-coupling platform for the efficient construction of C(sp)-C(sp) and C(sp)-C(sp) bonds from readily available alkyl bistriflimides. This methodology involves the assembly of two leaving groups on alkyl amines to form alkyl bistriflimides, followed by their effective coupling with a wide range of alkyl halides, alkyl pseudohalides, aryl halides, and alkenyl halides under electrochemical reductive conditions. Moreover, the successful application of electrochemical reductive relay cross-coupling and transition metal-free cross-electrophile coupling further demonstrates the versatility of alkyl bistriflimides as valuable building blocks in organic synthesis.
View Article and Find Full Text PDFChemistry
November 2024
College of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004, P.R. China.
Polyfluoroaryl ethers represent an important framework of biologically active molecules and materials. Owing to the strong bond dissociation energy of C-F bond, selectivity and other issues, transition metal-catalyzed synthesis of polyfluoroaryl ethers from perfluoroarenes via the activation of C-F bond is challenging and underdeveloped, as compared to the well-documented C-O bond formation starting from aryl iodides, aryl bromides or aryl chlorides. Herein, an unprecedented Pd-catalyzed defluorinative etherification for the synthesis of polyfluoroaryl ether skeletons using hydrobenzoxazoles as phenol surrogate, has been reported.
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