New modes of chemical reactivity are of high value to synthetic organic chemistry. In this vein, carbon-carbon (C-C) activation is an emerging field that offers new possibilities for synthesizing valuable complex molecules. This review discusses the pioneering stoichiometric discoveries in this field up to the most recent synthetic applications that apply catalytic transformations. Specifically, the review focuses on C-C activation in relatively unstrained systems, including stoichiometric reactions, chelation-directed and chelation-free catalytic reactions. While the field of C-C activation of relatively unstrained systems is underdeveloped, we expect that this review will provide insight into new developments and pave the path for robust, practical applications.
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http://dx.doi.org/10.1039/c4qo00053f | DOI Listing |
Nat Chem
December 2024
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, China.
Saturated N-heterocycles are ubiquitous structures among natural products and biologically active compounds. Therefore, the development of synthetic methods for the construction of N-heterocycles is of great importance in the synthetic community. Altering the ring system of these motifs to analogues with different ring sizes by employing molecular editing techniques would be highly appealing in medicinal chemistry.
View Article and Find Full Text PDFJ Phys Chem C Nanomater Interfaces
November 2024
Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, Berlin D-14195, Germany.
Nat Catal
April 2024
Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Constructive functionalization of unstrained aryl-aryl bonds has been a fundamental challenge in organic synthesis due to the inertness of these bonds. Here we report a split cross-coupling strategy that allows two-fold arylation with diverse aryl iodides through cleaving unstrained aryl-aryl bonds of common 2,2'-biphenols. The reaction is catalyzed by a rhodium complex and promoted by a removable phosphinite directing group and an organic reductant.
View Article and Find Full Text PDFJ Phys Chem C Nanomater Interfaces
October 2024
Department of Physical and Life Sciences, University of Huddersfield, Queensgate, Huddersfield HD1 3DH, U.K.
Nanocrystalline ceria exhibits significant redox activity and oxygen storage capacity. Any factor affecting its morphology can tune such activities. Strain is a promising method for controlling particle morphology, whether as core@shell structures, supported nanoparticles, or nanograins in nanocrystalline ceria.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai 200032, China.
The asymmetric functionalization of unstrained C(sp)-C(sp) bonds could be a powerful strategy to stereoselectively reconstruct the backbone of an organic compound, but such reactions are rare. Although allylic substitutions have been used frequently to construct C-C bonds by the cleavage of more reactive C-X bonds (X is usually an O atom of an ester) by transition metals, the reverse process that involves the replacement of a C-C bond with a C-heteroatom bond is rare and generally considered thermodynamically unfavorable. We show that an unstrained, inert allylic C-C σ bond can be converted to a C-N bond stereoselectively via a designed solubility-control strategy, which makes the thermodynamically unfavorable process possible.
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