A simple and efficient Mn-catalyzed acylation of amines is achieved using both acyl and alkoxy functions of unactivated esters with the liberation of molecular hydrogen as a sole byproduct. The present protocol provides an atom-economical and sustainable route for the synthesis of amides from esters by employing an earth-abundant manganese salt and inexpensive phosphine-free tridentate ligand.
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http://dx.doi.org/10.1021/acs.orglett.8b01305 | DOI Listing |
RSC Adv
August 2024
Flavors and Fragrance Engineering & Technology Research Center of Henan Province, College of Tobacco Science Henan Agricultural University Zhengzhou 450002 China
Herein, the direct oxidation of furfuryl alcohols and furfurals to the corresponding furoic acids is performed highly efficiently with potassium hydroxide as the base in the presence of a catalytic amount of PNP pincer manganese catalyst in dioxane. The manganese catalytic system can not only achieve the dehydrogenation conversion of furfuryl alcohols to prepare furoic acids but can also achieve the synthesis of furoic acids from furfurals under more moderate conditions and with less reaction time. In addition, the bifunctional furfuryl alcohols or furfurals can also be efficiently converted into dicarboxylic acid products under optimal reaction conditions.
View Article and Find Full Text PDFJ Am Chem Soc
July 2024
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
Direct site-selective and enantioselective oxyfunctionalization of C(sp)-H bonds to form alcohols with a general scope, with predictable selectivities, and in preparatively useful yields represents a paradigm shift in the standard logic of synthetic organic chemistry. However, the knowledge of either enzymatic or nonenzymatic asymmetric hydroxylation of tertiary C-H bonds for enantioenriched tertiary alcohol synthesis is sorely lacking. Here, we report a practical manganese-catalyzed enantio-differentiating hydroxylation of tertiary propargylic C-H bonds in acyclic systems, producing a wide range of structurally diverse enantioenriched tertiary propargyl alcohols in high efficiency with extremely efficient chemo- and enantio-discrimination.
View Article and Find Full Text PDFRSC Adv
April 2024
College of Pharmaceutical Sciences, Zhejiang University of Technology Hangzhou 310014 P. R. China
3d-Metal catalyzed borrowing hydrogen (BH) reactions represent powerful and environmentally friendly approaches for the direct coupling of alcohols with nitriles to assemble various important branched nitriles. The development of simple and efficient ligands is a crucial issue in this field. In this study, we designed a series of readily available ,-bidentate ligands that demonstrated good efficiency in the Mn-catalyzed BH reaction of alcohols and nitrile derivatives, yielding the targeted nitriles in moderate to good yields.
View Article and Find Full Text PDFAcc Chem Res
March 2024
Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom.
ConspectusAn understanding of the mechanistic processes that underpin reactions catalyzed by 3d transition metals is vital for their development as potential replacements for scarce platinum group metals. However, this is a significant challenge because of the tendency of 3d metals to undergo mechanistically diverse pathways when compared with their heavier congeners, often as a consequence of one-electron transfer reactions and/or intrinsically weaker metal-ligand bonds. We have developed and implemented a new methodology to illuminate the pathways that underpin C-H bond functionalization pathways in reactions catalyzed by Mn-carbonyl compounds.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2024
Department of Chemistry, Tsinghua University, Beijing, 100084, China.
The oxygen evolution reaction (OER), characterized by a four-electron transfer kinetic process, represents a significant bottleneck in improving the efficiency of hydrogen production from water electrolysis. Consequently, extensive research efforts have been directed towards identifying single-atom electrocatalysts with exceptional OER performance. Despite the comprehensive understanding of the OER mechanism, its application to other valuable synthetic reactions has been limited.
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