Rhodium(III)‐Catalyzed Intramolecular Hydroarylation, Amidoarylation, and Heck‐type Reaction: Three Distinct Pathways Determined by an Amide Directing Group

Davis, Tyler A.; Hyster, Todd K.; Rovis, Tomislav

doi:10.1002/ange.201307631

Cited by 49 publications

(8 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We undertook an initial comprehensive study involving simple alkenes tethered to the benzamide and benzoic acid systems at the meta position. 26,27 While this has the clear disadvantage of being a tethering strategy, we gained insights into the reaction and examined the reactivity of more complex stereochemically defined internal alkenes.…”

Section: Synthesis Of Isoquinolones Pyridones and Their Derivativesmentioning

confidence: 99%

Electronic and Steric Tuning of a Prototypical Piano Stool Complex: Rh(III) Catalysis for C–H Functionalization

2017

Self Cite

View full text Add to dashboard Cite

The history of transition metal catalysis is heavily steeped in ligand design, clearly demonstrating the importance of this approach. The intimate relationship between metal and ligand can profoundly affect the outcome of a reaction, often impacting selectivity, physical properties, and the lifetime of a catalyst. Importantly, this metal-ligand relationship can provide near limitless opportunities for reaction discovery. Over the past several years, transition-metal-catalyzed C-H bond functionalization reactions have been established as a critical foundation in organic chemistry that provides new bond forming strategies. Among the d-block elements, palladium is arguably one of the most popular metals to accomplish such transformations. One possible explanation for this achievement could be the broad set of phosphine and amine based ligands available in the chemist's toolbox compatible with palladium. In parallel, other metals have been investigated for C-H bond functionalization. Among them, pentamethylcyclopentadienyl (Cp*) Rh(III) complexes have emerged as a powerful mode of catalysis for such transformations providing a broad spectrum of reactivity. This approach possesses the advantage of often very low catalyst loading, and reactions are typically performed under mild conditions allowing broad functional group tolerance. Cp*Rh(III) is considered as a privileged catalyst and a plethora of reactions involving a C-H bond cleavage event have been developed. The search for alternative cyclopentadienyl based ligands has been eclipsed by the tremendous effort devoted to exploring the considerable scope of reactions catalyzed by Cp*Rh(III) complexes, despite the potential of this strategy for enabling reactivity. Thus, ligand modification efforts in Rh(III) catalysis have been an exception and research directed toward new rhodium catalysts has been sparse. Recently, chiral cyclopentadienyl ligands have appeared allowing enantioselective Rh(III)-catalyzed C-H functionalization reactions to be performed. Alongside chiral ligands, an equally important collection of achiral cyclopentadienyl-derived ligands have also emerged. The design of this new set of ligands for rhodium has already translated to significant success in solving inherent problems of reactivity and selectivity encountered throughout the development of new Rh(III)-catalyzed transformations. This Account describes the evolution of cyclopentadienyl ligand skeletons in Rh(III)-catalysis since the introduction of pentamethylcyclopentadienyl ligands to the present. Specific emphasis is placed on reactivity and synthetic applications achieved with the new ligands with the introduction of achiral mono-, di-, or pentasubstituted cyclopentadienyl ligands exhibiting a stunning effect on reactivity and selectivity. Furthermore, an underlying question when dealing with ligand modification strategies is to explain the reason one ligand outperforms another. Conjecture and speculation abound, but extensive characterization of their steric and electronic properties has ...

show abstract

Section: Synthesis Of Isoquinolones Pyridones and Their Derivativesmentioning

confidence: 99%

Electronic and Steric Tuning of a Prototypical Piano Stool Complex: Rh(III) Catalysis for C–H Functionalization

2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…[46] Three distinct pathways are made possible based on both directing group and conditions. After intramolecular alkene insertion, protonolysis, β-hydride elimination or reductive elimination allow access to different structural scaffolds (Table 3).…”

Section: Rhodium Catalysismentioning

confidence: 99%

A Simple and Versatile Amide Directing Group for C−H Functionalizations

et al. 2016

View full text Add to dashboard Cite

Achieving selective C–H activation at a single and strategic site in the presence of multiple C–H bonds can provide a powerful and generally useful retrosynthetic disconnection. In this context, the directing group serves as a compass to guide the transition metal to C–H bonds using distance and geometry as powerful recognition parameters to distinguish between proximal and distal C–H bonds. However, the installation and removal of directing groups is a practical drawback. To improve the utility of this approach, one can seek solutions in three directions. First, simplifying the directing group; Second, use of common functional groups or protecting groups as directing groups; Third, attaching the directing group to substrates via a transient covalent bond to render directing groups catalytic. This review describes the rational development of an extremely simple and yet broadly applicable directing group for Pd(II), Rh(III) and Ru(II) catalysts, namely, the N-methoxy amide (CONHOMe). Through collective efforts in the community, a wide range of C–H activation transformations using this type of simple directing groups has been developed.

show abstract

mentioning

confidence: 99%

“…Intriguingly, the analogous asymmetric annulations have been realized by the directing-group-assisted C À H activation promoted by either a rhodium(I) [17] or rhodium-(III) [18] catalyst (Scheme 1 b). [19] Herein, we describe a ruthenium-catalyzed enantioselective synthesis of chiral 3,3-disub- stituted 2,3-dihydrobenzofuran by the TDG strategy (Scheme 1 c). [20] A series of 2,3-dihydrobenzofurans with chiral all-carbon quaternary stereocenters were obtained in high yields (up to 98 %) and high enantioselectivities (up to > 99 % ee) promoted by catalytic amounts of [Ru(p-cymene)Cl 2 ] 2 and a cheap chiral amine.…”

mentioning

confidence: 99%

Ruthenium(II)‐Catalyzed Asymmetric Inert C−H Bond Activation Assisted by a Chiral Transient Directing Group

Liu

Vasamsetty

et al. 2020

Angew Chem Int Ed

View full text Add to dashboard Cite

A ruthenium(II)‐catalyzed asymmetric intramolecular hydroarylation assisted by a chiral transient directing group has been developed. A series of 2,3‐dihydrobenzofurans bearing chiral all‐carbon quaternary stereocenters have been prepared in remarkably high yields (up to 98 %) and enantioselectivities (up to >99 % ee). By this methodology, a novel asymmetric total synthesis of CB2 receptor agonist MDA7 has been successfully developed.

show abstract

Rhodium(III)‐Catalyzed Intramolecular Hydroarylation, Amidoarylation, and Heck‐type Reaction: Three Distinct Pathways Determined by an Amide Directing Group

Cited by 49 publications

References 41 publications

Electronic and Steric Tuning of a Prototypical Piano Stool Complex: Rh(III) Catalysis for C–H Functionalization

Electronic and Steric Tuning of a Prototypical Piano Stool Complex: Rh(III) Catalysis for C–H Functionalization

A Simple and Versatile Amide Directing Group for C−H Functionalizations

Ruthenium(II)‐Catalyzed Asymmetric Inert C−H Bond Activation Assisted by a Chiral Transient Directing Group

Contact Info

Product

Resources

About