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Open accessJournal ArticleDOI: 10.1002/ANIE.202017359

Rhoda‐Electrocatalyzed Bimetallic C–H Oxygenation by Weak O‐Coordination

02 Mar 2021-Angewandte Chemie (Wiley)-Vol. 60, Iss: 24, pp 13264-13270
Abstract: Rhodium-electrocatalyzed arene C-H oxygenation by weakly O- coordinating amides and ketones have been established by bimetallic electrocatalysis. Likewise, diverse dihydrooxazinones were selectively accessed by the judicious choice of current, enabling twofold C-H functionalization. Detailed mechanistic studies by experiment, mass spectroscopy and cyclovoltammetric analysis provided support for an unprecedented electrooxidation-induced C-H activation by a bimetallic rhodium catalysis manifold.

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6 results found

Journal ArticleDOI: 10.1021/ACS.ORGLETT.1C01224
Amrita Das1, Naoto Chatani1Institutions (1)
14 May 2021-Organic Letters
Abstract: The Rh-catalyzed C-H alkylation of benzylamine derivatives with unactivated 1-alkenes that proceeds via a picolinamide directing group is reported. The crucial role of an acid additive in this transformation is confirmed. Aromatic acids showed high linear selectivity, and aliphatic acids provided branched alkylation products as the major product. The reaction has a broad scope for benzylamines and alkenes. Deuterium labeling experiments suggest that a Rh-carbene intermediate is involved in the case of linear product formation. A different reaction pathway, however, appears to be involved in the case of branched alkylation products, and this pathway also appeared to be a minor pathway in linear-selective reactions.

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Topics: Alkylation (58%), Benzylamine (52%), Catalysis (50%) ... read more

2 Citations

Journal ArticleDOI: 10.1039/D1GC03187B
Zi-Chen Wang1, Rui-Tao Li1, Qiang Ma1, Jia-Yi Chen2  +4 moreInstitutions (2)
12 Oct 2021-Green Chemistry
Abstract: Herein, electrochemically driven, Rh(III)-catalyzed regioselective annulations of arenes with alkynes have been established. The strategy, combining the use of a rhodium catalyst with electricity, not only avoids the need for using a stoichiometric amount of external oxidant, but also ensures that the transformations proceed under mild and green conditions, which enable broad functional group compatibility with a variety of substrates, including drugs and pharmaceutical motifs. Moreover, the electrolysis reaction was made operationally simple by employing an undivided cell, and proceeds efficiently in aqueous solution in air.

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Open accessJournal ArticleDOI: 10.1021/ACS.JOC.1C02275
Gaurav Shukla1, Priya Saha1, Pragya Pali1, Keshav Raghuvanshi2  +1 moreInstitutions (2)
Abstract: We have developed an electrochemical approach for the synthesis of fully substituted 1,2,3-thiadiazoles from α-phenylhydrazones at room temperature, which is very challenging and complementary to the conventional thermal reactions. The key step involves anodic oxidation of phenylhydrazone derivatives at a constant current followed by N,S-heterocyclization. The protocol is remarkable in that it is free of a base and free of an external oxidant and can be converted to a gram scale for postsynthetic drug development with functional thiadiazoles. Most importantly, the electrochemical transformation reflected efficient electro-oxidation with an operationally friendly easy procedure with ample functional molecules. Cyclic voltammograms support the mechanism of this electro-oxidative cyclization process.

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Topics: Thiadiazoles (50%)


88 results found

Journal ArticleDOI: 10.1002/ANIE.200902996
21 Dec 2009-Angewandte Chemie
Abstract: The area of transition-metal-catalyzed direct arylation through cleavage of CH bonds has undergone rapid development in recent years, and is becoming an increasingly viable alternative to traditional cross-coupling reactions with organometallic reagents In particular, palladium and ruthenium catalysts have been described that enable the direct arylation of (hetero)arenes with challenging coupling partners—including electrophilic aryl chlorides and tosylates as well as simple arenes in cross-dehydrogenative arylations Furthermore, less expensive copper, iron, and nickel complexes were recently shown to be effective for economically attractive direct arylations

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2,290 Citations

Open accessJournal ArticleDOI: 10.1021/AR200185G
Abstract: Reactions that convert carbon–hydrogen (C–H) bonds into carbon–carbon (C–C) or carbon–heteroatom (C–Y) bonds are attractive tools for organic chemists, potentially expediting the synthesis of target molecules through new disconnections in retrosynthetic analysis. Despite extensive inorganic and organometallic study of the insertion of homogeneous metal species into unactivated C–H bonds, practical applications of this technology in organic chemistry are still rare. Only in the past decade have metal-catalyzed C–H functionalization reactions become more widely utilized in organic synthesis.Research in the area of homogeneous transition metal–catalyzed C–H functionalization can be broadly grouped into two subfields. They reflect different approaches and goals and thus have different challenges and opportunities. One approach involves reactions of completely unfunctionalized aromatic and aliphatic hydrocarbons, which we refer to as “first functionalization”. Here the substrates are nonpolar and hydrophobic a...

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Topics: Retrosynthetic analysis (51%)

2,097 Citations

Journal ArticleDOI: 10.1038/NCHEM.1607
Joanna Wencel-Delord1, Frank Glorius2Institutions (2)
01 May 2013-Nature Chemistry
Abstract: The beginning of the twenty-first century has witnessed significant advances in the field of C-H bond activation, and this transformation is now an established piece in the synthetic chemists' toolbox. This methodology has the potential to be used in many different areas of chemistry, for example it provides a perfect opportunity for the late-stage diversification of various kinds of organic scaffolds, ranging from relatively small molecules like drug candidates, to complex polydisperse organic compounds such as polymers. In this way, C-H activation approaches enable relatively straightforward access to a plethora of analogues or can help to streamline the lead-optimization phase. Furthermore, synthetic pathways for the construction of complex organic materials can now be designed that are more atom- and step-economical than previous methods and, in some cases, can be based on synthetic disconnections that are just not possible without C-H activation. This Perspective highlights the potential of metal-catalysed C-H bond activation reactions, which now extend beyond the field of traditional synthetic organic chemistry.

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1,615 Citations

Journal ArticleDOI: 10.1039/C1CS15013H
Abstract: Metal-catalysed C–H bond functionalisation has had a significant impact on how chemists make molecules. Translating the methodological developments to their use in the assembly of complex natural products is an important challenge for the continued advancement of chemical synthesis. In this tutorial review, we describe selected recent examples of how the metal-catalysed C–H bond functionalisation has been able to positively affect the synthesis of natural products.

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1,245 Citations

Open accessJournal ArticleDOI: 10.1021/ACS.CHEMREV.7B00397
Ming Yan1, Yu Kawamata1, Phil S. Baran1Institutions (1)
09 Oct 2017-Chemical Reviews
Abstract: Electrochemistry represents one of the most intimate ways of interacting with molecules. This review discusses advances in synthetic organic electrochemistry since 2000. Enabling methods and synthetic applications are analyzed alongside innate advantages as well as future challenges of electroorganic chemistry.

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1,208 Citations

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