Amidation of Saturated C−H Bonds Catalyzed by Electron-Deficient Ruthenium and Manganese Porphyrins. A Highly Catalytic Nitrogen Atom Transfer Process

Yu, Xiao‐Qi; Huang, Jie‐Sheng; Zhou, Xiangge; Che, Chi‐Ming

doi:10.1021/ol000107r

Cited by 301 publications

(115 citation statements)

References 11 publications

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“…In an important advance, Che has demonstrated that PhI(OAc) 2 and TsNH 2 can replace the capricious TsN=IPh reagent for C-H insertion reactions with manganese and ruthenium porphyrins (Scheme 17.11) [56]. A similar discovery was made contemporaneously by Espino and Du Bois for intramolecular C-H amination of carbamate and sulfamate esters with rhodium(II) catalysts (vide infra) [57].…”

Section: Intermolecular C-h Amination With Other Metalsmentioning

confidence: 87%

Rhodium(II)‐Catalyzed Oxidative Amination

Espino

Bois

2005

Modern Rhodium‐Catalyzed Organic Reactions

105

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17 Rhodium(II)-Catalyzed Oxidative Amination 380 Scheme 17.1 Copper-catalyzed decomposition of arylsulfonyl azides. Scheme 17.2 Intramolecular C-H amination of an iminoiodinane. 17.3 Intermolecular C-H Amination with Rhodium(II) Catalysts 381 Scheme 17.3 Metal porphyrin-catalyzed allylic amination. Scheme 17.4 C-H amination by a radical-rebound mechanism. 17 Rhodium(II)-Catalyzed Oxidative Amination 382 Scheme 17.5 Rhodium-catalyzed N-atom transfer using NsN=IPh. Scheme 17.6 Stereospecific C-H amination under rhodium-catalyzed conditions. 17.3 Intermolecular C-H Amination with Rhodium(II) Catalysts 383 Scheme 17.7 Radical clock study of metallo-nitrene C-H insertion. Scheme 17.8 Intermolecular C-H insertion by chiral rhodium catalysts. 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 385 Scheme 17.11 Allylic and benzylic amination using PhI(OAc) 2 . 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 387 Tab. 17.1 C-H amination of 18 carbamate esters. Entry Substrate Product Entry Substrate Product 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 389 Scheme 17.14 Ketone formation by 28 alcohol-derived carbamates. 17.7 Enantioselective C-H Insertion with Sulfamate Esters 401 Scheme 17.29 Oxidative cyclization of unsaturated sulfonamides. Scheme 17.30 Preliminary investigations of asymmetric C-H amination. 17.11 Applications of C-H Amination in Synthesis 407 17.11 Applications of C-H Amination in Synthesis 409 Scheme 17.39 Asymmetric synthesis of (-)-tetrodotoxin. 17 Rhodium(II)-Catalyzed Oxidative Amination 410 Scheme 17.40 Nucleophilic ring opening of N-acylated oxathiazinanes. Scheme 17.41 Nickel-catalyzed cross-coupling of phenol-derived sulfamate esters.

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Section: Intermolecular C-h Amination With Other Metalsmentioning

confidence: 87%

Rhodium(II)‐Catalyzed Oxidative Amination

Espino

Bois

2005

Modern Rhodium‐Catalyzed Organic Reactions

105

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“…Generally, the most broadly used precursors to the transient metal nitrenes have been aryliminoiodinanes, which are decomposed by a suitable metal complex 77 . In the syntheses described here, the aryliminoiodinanes are produced in situ from the corresponding amine, which makes the overall transformations even more attractive 78 nitrenoids 80,81 . By conducting this nitrene insertion with chiral dirhodium catalyst Rh 2 (S-TCPTAD) 4 , enantioselective transformations can be achieved, as illustrated in Fig.…”

Section: C-h Functionalization By Metal Nitrenoidsmentioning

confidence: 99%

Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion

Davies

Manning

2008

Nature

2,179

812

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Novel reactions that can selectively functionalize carbon-hydrogen bonds are of intense interest to the chemical community because they offer new strategic approaches for synthesis. A very promising 'carbon-hydrogen functionalization' method involves the insertion of metal carbenes and nitrenes into C-H bonds. This area has experienced considerable growth in the past decade, particularly in the area of enantioselective intermolecular reactions. Here we discuss several facets of these kinds of C-H functionalization reactions and provide a perspective on how this methodology has affected the synthesis of complex natural products and potential pharmaceutical agents.I n 2006, 31 new chemical entities were introduced to the world pharmaceutical market and 2,075 molecules were in phase I or II of clinical development 1 . The majority of these were smallmolecule (relative molecular mass ,1,000) organic compounds 2 . As knowledge about the specific interactions of drugs in vivo increases, often so does the structural complexity of new drug targets. A major obstacle to the development of such drugs is the difficulty associated with synthesizing large quantities in an economical fashion, because complex multi-step syntheses are usually required. In the general media, it is often overlooked that the accessibility of the components required for these new treatments will often govern their eventual success or failure. Likewise, a design element of any pharmaceutical agent is the expectation that the target compounds can be made economically. Therefore, new strategies for synthesis can become enabling technologies, making available new targets and materials that would have been previously out of range. For example, new methodologies such as metal-catalysed crosscoupling 3 and olefin metathesis 4-6 have rapidly become central transformations in the synthesis of new pharmaceutical agents. Selective C-H functionalization is a class of reactions that could lead to a paradigm shift in organic synthesis, relying on selective modification of ubiquitous C-H bonds of organic compounds instead of the standard approach of conducting transformations on pre-existing functional groups. The reactive sites in each type of transformation are very different, as illustrated in Fig. 1.The many opportunities associated with C-H functionalization has made this field an active area of research. Organometallic chemists have focused much attention on developing 'C-H activation' strategies, whereby a highly reactive metal complex inserts into a C-H bond, activating the system for subsequent transformations 7-9 . One of the major challenges associated with this chemistry has been to render it catalytic in the metal complex 10 . A partial solution to this problem has been to use neighbouring functionality to direct less reactive metal complexes to the site for functionalization. Numerous reviews have been written about this method for C-H functionalization [11][12][13][14][15][16][17] . Here, however, we highlight another approach, in which a divalent c...

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“…[186] The problems generally associated with the isolation and purification of nonstabilized iminoiodananes [187] was circumvented by Che and co-workers with the development of an in situ protocol that generated nitrenes from TsNH 2 and PhI(OAc) 2 in the presence of a manganese-porphyrin catalyst. [188] The practicality of C À H aminations employing metal nitrenes was dramatically increased by a report from Espino and Du Bois, who detailed a highly chemo-and stereoselective process whereby oxazolidinones 217 could be prepared from carbamates 216 through an intramolecular CÀH amination (Scheme 91). [189] The reactive species is believed to be a rhodium-nitrene intermediate arising from an iminoiodinane formed in a reaction between the carbamate and a hypervalent iodine reagent.…”

Section: Metal-catalyzed C à H Activationmentioning

confidence: 99%

Chemoselectivity and the Curious Reactivity Preferences of Functional Groups

2009

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Achieving high levels of chemoselectivity has been the Achilles' heel of chemical synthesis. The excitement generated by the successful realization of chemoselective strategies underscores the painstaking efforts to define a set of conditions conducive to selection among the available reaction pathways. We discuss in this Review various aspects of chemoselectivity that have been addressed in a range of synthetic methods over the past decade. We have focused on the proposed mechanistic basis of the reactions under consideration in an attempt to categorize them and highlight the key concepts that have been emerging on the basis of these studies. Our overview of recent advances in chemoselective processes suggests that significant progress has been made, but a lot of challenges lie ahead.

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Amidation of Saturated C−H Bonds Catalyzed by Electron-Deficient Ruthenium and Manganese Porphyrins. A Highly Catalytic Nitrogen Atom Transfer Process

Cited by 301 publications

References 11 publications

Rhodium(II)‐Catalyzed Oxidative Amination

Rhodium(II)‐Catalyzed Oxidative Amination

Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion

Chemoselectivity and the Curious Reactivity Preferences of Functional Groups

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