Efficient Diastereoselective Intermolecular Rhodium‐Catalyzed CH Amination

Liang, Chengzhen; Robert‐Peillard, Fabien; Fruit, Corinne; Müller, Paul; Dodd, Robert H.; Dauban, Philippe

doi:10.1002/ange.200601248

Cited by 74 publications

(19 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…39 Impressive diastereocontrol has been reported by Müller, Dodd, Dauban and co-workers in the enantioselective C-H amination of indene (>99% de) in 80% yield with Rh 2 (S-NTTL) 4 (21a). High yield and enantiocontrol was also recently reported by Davies and co-workers in a similar reaction using the newly developed Rh 2 (S-TCPTAD) 4 (20b) (Scheme 6).…”

Section: Phthalimide Derived Complexes-ikegami Hashimoto and Co-workmentioning

confidence: 93%

High symmetry dirhodium(II) paddlewheel complexes as chiral catalysts

Hansen

Davies

2008

Coordination Chemistry Reviews

236

150

View full text Add to dashboard Cite

The design and use of chiral dirhodium(II) paddlewheel complexes as catalysts for asymmetric metal carbenoid and metal nitrenoid reactions, and as Lewis acids have become areas of considerable interest during the past two decades. The metal carbenoid chemistry is especially versatile, encompassing transformations such as C-H insertions, cyclopropanations and ylide formation. A number of different classes of dirhodium(II) catalysts have been found to be broadly effective in this chemistry. This review will highlight that many of these catalysts have higher symmetry than the individual chiral ligands themselves. An introduction of theoretical aspects concerning the structure and symmetry of chiral dirhodium(II) complexes will be given followed by an overview of the major classes of catalysts developed to date. Some representative examples of the synthetic potential of these catalysts will also be discussed.

show abstract

Section: Phthalimide Derived Complexes-ikegami Hashimoto and Co-workmentioning

confidence: 93%

High symmetry dirhodium(II) paddlewheel complexes as chiral catalysts

Hansen

Davies

2008

Coordination Chemistry Reviews

236

150

View full text Add to dashboard Cite

show abstract

“…12) [83][84][85] . Enantioselective intermolecular reactions of metal nitrenes are less developed than the parallel reactions of metal carbenes, although some significant examples have been reported 81,82,86,87 . A conceptually interesting approach to stereoselective intermolecular nitrene chemistry involves the use of a chiral sulphonamide (compound 48) as the amine source in the reactions.…”

Section: C-h Functionalization By Metal Nitrenoidsmentioning

confidence: 99%

“…A conceptually interesting approach to stereoselective intermolecular nitrene chemistry involves the use of a chiral sulphonamide (compound 48) as the amine source in the reactions. Exceptionally high diastereoselectivity can be obtained in matched reactions between the appropriate enantiomers of a chiral sulphonamide and a chiral rhodium catalyst 87 . Given the ubiquity of nitrogen atoms in biologically active compounds, C2H amination as an enabling technology in pharmaceutical synthesis has broad potential.…”

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

View full text Add to dashboard Cite

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...

show abstract

“…[11] These reports propelled N-atom transfer substantially forward to enable enantioselective aziridination [12] and the regio-, [13] diastereo-, [14] and enantioselective [15] functionalization of aliphatic C-H bonds. Despite these remarkable advances, the formation of sp 2 C-N bonds using iminoiodinanes as the source of the nitrogen-atom has been elusive.…”

Section: Isomerization Of Pre-existing N-heterocyclesmentioning

confidence: 99%

Transition Metal‐Catalyzed Formation of N‐Heterocycles via Aryl‐ or Vinyl C–H Bond Amination

2011

View full text Add to dashboard Cite

The construction of N‐heterocycles remains a fertile area of research because of their ubiquitous occurrence in biologically active small molecules and materials. Their ubiquitous nature has motivated the development of methods to streamline their synthesis. Formation of the C–N bond via transition metal‐functionalization of the aryl or vinyl C–H bond simplifies N‐heterocycle synthesis by minimizing the manipulation of functional groups. Transition metal‐catalyzed C–H bond amination can be accomplished through two strategies: the activation of the N‐atom or activation of the C–H bond. This microreview examines the recent advances in applying these two strategies for the functionalization of sp2 C–H bonds and is organized by the source of nitrogen atom.

show abstract

Efficient Diastereoselective Intermolecular Rhodium‐Catalyzed CH Amination

Cited by 74 publications

References 71 publications

High symmetry dirhodium(II) paddlewheel complexes as chiral catalysts

High symmetry dirhodium(II) paddlewheel complexes as chiral catalysts

Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion

Transition Metal‐Catalyzed Formation of N‐Heterocycles via Aryl‐ or Vinyl C–H Bond Amination

Contact Info

Product

Resources

About