Inexpensive cobalt-catalyzed oxidative C-H functionalization has emerged as a powerful tool for the construction of C-C and C-Het bonds, which offers unique potential for transformative applications to modern organic synthesis. In the early stage, these transformations typically required stoichiometric and toxic transition metals as sacrificial oxidants; thus, the formation of metal-containing waste was inevitable. In contrast, naturally abundant molecular O has more recently been successfully employed as a green oxidant in cobalt catalysis, thus considerably improving the sustainability of such transformations. Recently, a significant momentum was gained by the use of electricity as a sustainable and environmentally benign redox reagent in cobalt-catalyzed C-H functionalization, thereby preventing the consumption of cost-intensive chemicals while at the same time addressing the considerable safety hazards related to the use of molecular oxygen in combination with flammable organic solvents. Considering the unparalleled potential of the aforementioned approaches for sustainable green synthesis, this Review summarizes the recent progress in cobalt-catalyzed oxidative C-H activation until early 2020.
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http://dx.doi.org/10.1002/cssc.202000024 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Shanghai Institute of Organic Chemistry, State Key Lab of Organometallic Chemistry, 345 Lingling Road, 200032, Shanghai, CHINA.
A dual photoredox/cobalt-catalyzed protocol for chemo-, regio-, diastereo- and enantioselective reductive coupling of 1,1-disubstituted allenes and cyclobutenes through chemo-, regio-, diastereo- and enantioselective oxidative cyclization followed by stereoselective protonation promoted by a chiral phosphine-cobalt complex is presented. Such process represents an unprecedented reaction pathway for cobalt catalysis that enables selective transformation of the less sterically congested alkenes of 1,1-disubstituted allenes with cyclobutenes, incorporating a broad scope of tetrasubstituted alkenes into the cyclobutane scaffolds in up to 86% yield, >98:2 chemo- and regioselectivity, >98:2 dr and >99.5:0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
EaStCHEM, School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK.
A highly enantioselective cobalt-catalyzed semipinacol rearrangement of symmetric α,α-diarylallylic alcohols is disclosed. A chiral cobalt-salen catalyst generates a highly electrophilic carbocation surrogate following hydrogen atom transfer and radical-polar crossover steps. This methodology provides access to enantioenriched α-aryl ketones through invertive displacement of a cobalt(IV) complex during 1,2-aryl migration.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China.
Inherently chiral calixarenes have garnered significant attention due to their distinctive properties, yet the development of efficient catalytic asymmetric synthesis methods remains a critical challenge. Herein, we report the asymmetric synthesis of calix[4]arenes featuring inherent or both inherent and axial chirality via a cobalt-catalyzed C-H activation/annulation strategy in high yield with excellent enantio- and diastereoselectivity (up to >99 % ee and >20 : 1 dr). Electrooxidation was also suitable for this transformation to obviate the sacrificial metal oxidants, underscoring the environmentally friendly potential of this approach.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai, China.
Catalytic regio-, diastereo- and enantioselective reductive coupling of 1,3-dienes and aldehydes through regio- and enantioselective oxidative cyclization followed by regio- and diastereoselective protonation promoted by a chiral phosphine-cobalt complex is presented. Such processes represent an unprecedented reaction pathway for cobalt catalysis that enable selective transformation of the more substituted alkene in 1,3-dienes, affording a broad scope of bishomoallylic alcohols without the need of pre-formation of stoichiometric amounts of sensitive organometallic reagents in up to 98 % yield, >98 : 2 regioselectivity, >98 : 2 dr and 98 : 2 er. Application of this method to construction of axial stereogenicity and deuterated stereogenic center provided a wide range of multifunctional chiral building blocks that are otherwise difficult to access.
View Article and Find Full Text PDFInt J Mol Sci
July 2024
Faculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego St. 8, 61-614 Poznan, Poland.
A method for the reduction of aldehydes with pinacolborane catalyzed by pincer cobalt complexes based on a triazine backbone is developed in this paper. The presented methodology allows for the transformation of several aldehydes bearing a wide range of electron-withdrawing and electron-donating groups under mild conditions. The presented procedure allows for the direct one-step hydrolysis of the obtained intermediates to the corresponding primary alcohols.
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