Rhodium(<scp>iii</scp>)-catalysed decarbonylative annulation through C–H activation: expedient access to aminoisocoumarins by weak coordination

Mayakrishnan, Sivakalai; Arun, Y.; Maheswari, Narayanan Uma; Perumal, Paramasivan T.

doi:10.1039/c8cc07167e

Cited by 23 publications

(9 citation statements)

References 53 publications

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“…293-309) for both bond lengths and angles show that the differences between the two symmetry-independent molecules are of a statistical nature. For both compounds, the bond lengths and angles are close to those observed for a similar structure (Mayakrishnan et al, 2018). In both compounds, there is an intramolecular N-HÁ Á ÁO hydrogen bond present in each molecule forming an S(6) ring motif: see Table 1 and Fig.…”

Section: Structural Commentarysupporting

confidence: 74%

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Crystal structures of two new isocoumarin derivatives: 8-amino-6-methyl-3,4-diphenyl-1H-isochromen-1-one and 8-amino-3,4-diethyl-6-methyl-1H-isochromen-1-one

et al. 2019

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The title compounds, 8-amino-6-methyl-3,4-diphenyl-1H-isochromen-1-one, C22H17NO2, (I), and 8-amino-3,4-diethyl-6-methyl-1H-isochromen-1-one, C14H17NO2, (II), are new isocoumarin derivatives in which the isochromene ring systems are planar. Compound II crystallizes with two independent molecules (A and B) in the asymmetric unit. In I, the two phenyl rings are inclined to each other by 56.41 (7)° and to the mean plane of the 1H-isochromene ring system by 67.64 (6) and 44.92 (6)°. In both compounds, there is an intramolecular N—H...O hydrogen bond present forming an S(6) ring motif. In the crystal of I, molecules are linked by N—H...π interactions, forming chains along the b-axis direction. A C—H...π interaction links the chains to form layers parallel to (100). The layers are then linked by a second C—H...π interaction, forming a three-dimensional structure. In the crystal of II, the two independent molecules (A and B) are linked by N—H...O hydrogen bonds, forming –A–B–A–B– chains along the [101] direction. The chains are linked into ribbons by C—H...π interactions involving inversion-related A molecules. The latter are linked by offset π–π interactions [intercentroid distances vary from 3.506 (1) to 3.870 (2) Å], forming a three-dimensional structure.

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Section: Structural Commentarysupporting

confidence: 74%

“…amino-1H-isochromen-1-ones gave only one hit, viz. 8-amino-3,4-bis(4-methoxyphenyl)-1H-isochromen-1-one (CSD refcode NIKMAY; Mayakrishnan et al, 2018). The conformation of this molecule is slightly different from that of compound (I).…”

Section: Hirshfeld Surface Analysismentioning

confidence: 99%

Crystal structures of two new isocoumarin derivatives: 8-amino-6-methyl-3,4-diphenyl-1H-isochromen-1-one and 8-amino-3,4-diethyl-6-methyl-1H-isochromen-1-one

et al. 2019

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“…Recently, Uma Maheswari, Perumal, et al reported the Rh-catalyzed decarbonylative annulation of the less-strained isatoic anhydrides 174 with alkynes for the synthesis of aminoisocoumarins 177 (Scheme ). In this process, the weakly coordinating anhydrides facilitated the C–H activation to deliver the five-membered rhodacyclic intermediate 175 . Subsequent protonation and cyclization led to C–N bond cleavage and the formation of intermediate 176 , which underwent decarbonylation, insertion of the alkyne, and reductive elimination to afford the desired products 177 .…”

Section: Decarbonylation With Cleavage Of the C(acyl)–o/c(acyl)–c Bondsmentioning

confidence: 99%

Selective Decarbonylation via Transition-Metal-Catalyzed Carbon–Carbon Bond Cleavage

et al. 2020

Chem. Rev.

194

123

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Transition-metal-catalyzed decarbonylation via carbon−carbon bond cleavage is an essential synthetic methodology. Given the ubiquity of carbonyl compounds, the selective decarbonylative process offers a distinct synthetic strategy using carbonyl groups as "traceless handles". This reaction has been significantly developed in recent years in many respects, including catalytic system development, mechanistic understanding, substrate scope, and application in the synthesis of complex functional molecules. Therefore, this review aims to summarize the recent progress on transition-metal-catalyzed decarbonylative process, from the discovery of new transformations to the understanding of reaction mechanisms, to reveal the great achievements and potentials in this field. The contents of this review are categorized by the type of chemical bond cleavage in the decarbonylative process. The main challenges and opportunities of the decarbonylative process are also examined with the goal of expanding the application range of decarbonylation reactions.

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“…Similarly, Perumal and coworkers reported a regioselective decarbonylative cyclization of readily available isatoic anhydride 275 and an alkyne to afford biologically important 8-aminoisocoumarin 277 catalyzed by Rh complex (Scheme 45). [50] Electron-poor alkynes reacted slowly with a lower yield than electron-rich alkynes. A directed ortho-CÀ H activation of the rhodium complex generated a metalacycle intermediate 275 a.…”

Section: Addition To Coà X Bondmentioning

confidence: 99%

Dual Functionalization of Alkynes Utilizing the Redox Characteristics of Transition Metal Catalysts

2021

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Tri-and tetrasubstituted alkene scaffolds are prominent building blocks in many bioactive natural products, drug molecules, and key intermediates in various synthetic transformations. The dual functionalization of alkynes promises an easy introduction of functional groups across the triple bond with a high step and atom economy, exemplifying a class of reactions to construct tri-and tetrasubstituted alkene scaffolds. This review discusses the versatility and advances in the transition metal-catalyzed redox dual functionalization of alkynes, their unique mechanistic features, and the synthetic applications of the methodology. This collection focuses on the formation of simultaneous CÀ C/ CÀ X bonds involving various oxidation states of the metals in the catalytic cycle. Apart from the classical redox reactivity, radical-mediated functionalizations are also discussed in detail.

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Rhodium(iii)-catalysed decarbonylative annulation through C–H activation: expedient access to aminoisocoumarins by weak coordination

Cited by 23 publications

References 53 publications

Crystal structures of two new isocoumarin derivatives: 8-amino-6-methyl-3,4-diphenyl-1H-isochromen-1-one and 8-amino-3,4-diethyl-6-methyl-1H-isochromen-1-one

Crystal structures of two new isocoumarin derivatives: 8-amino-6-methyl-3,4-diphenyl-1H-isochromen-1-one and 8-amino-3,4-diethyl-6-methyl-1H-isochromen-1-one

Selective Decarbonylation via Transition-Metal-Catalyzed Carbon–Carbon Bond Cleavage

Dual Functionalization of Alkynes Utilizing the Redox Characteristics of Transition Metal Catalysts

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