Recent advances in transition-metal-catalyzed Büchner reaction of alkynes

Ma, Guang; Wei, Kua-Fei; Song, Man Suk; Dang, Yu-Li; Yang, Yongrong; Han, Bing; Su, Hui; Shen, Wen-Bo

doi:10.1039/d3ob00654a

Cited by 3 publications

(3 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recent years have observed the successful development of elegant domino reactions through furyl metal carbene intermediates, involving various reaction mechanisms such as carbene/alkyne metathesis, [1f] ring-opening/intramolecular cyclization of zwitterionic intermediates, semi-pinacol rearrangement, [38] Büchner reaction, [39] and carbene oxidation.…”

Section: Domino Reaction Via Furyl Metal Carbenesmentioning

confidence: 99%

Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes

Cho,

Kim

2024

Asian J Org Chem

View full text Add to dashboard Cite

Enynones and enynals represent donor‐type carbene precursors that efficiently form furyl metal carbenes via a catalytic intramolecular 5‐exo‐dig cyclization and rearrangement cascade, in a 100% atom‐economical manner, using various metals. These furyl metal carbenes have been successfully utilized in numerous carbene reactions, including metal carbene X–H insertion, cyclopropanations, metathesis, and cross‐coupling, demonstrating a broad reaction scope and efficiency in constructing highly functionalized furans. Recent years have witnessed significant advancements in transformations involving furyl metal carbenes, especially in asymmetric carbene insertion reactions, domino reactions involving zwitterionic intermediates, various rearrangement strategies, and their application in synthesizing functional materials and drug candidates. In this review, we summarize recent progress in furyl metal carbene reactions generated from enynones and enynals, focusing on the synthesis of highly functionalized furans.

show abstract

Section: Domino Reaction Via Furyl Metal Carbenesmentioning

confidence: 99%

Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes

Cho,

Kim

2024

Asian J Org Chem

View full text Add to dashboard Cite

show abstract

“…4 While these carbene/nitrene insertions are attractive, achieving selectivity poses a significant challenge. 5 In recent years, many controllable and selective skeletal modifications for benzenoid aromatics have been developed. Several unique methods for the ring expansion of benzenoids have been reported.…”

mentioning

confidence: 99%

“…Additionally, Beach and colleagues discovered that nitrene could be inserted in the benzene ring to achieve ring expansion transformation as well . While these carbene/nitrene insertions are attractive, achieving selectivity poses a significant challenge . In recent years, many controllable and selective skeletal modifications for benzenoid aromatics have been developed.…”

mentioning

confidence: 99%

Diversification of Naphthol Skeletons Triggered by Aminative Dearomatization

Li,

Wang,

Zhang

et al. 2024

Org. Lett.

View full text Add to dashboard Cite

A silver-catalyzed aminative dearomatization of naphthols has been developed and integrated into a stepwise approach for subsequent skeletal diversifications including ring expansion, ring opening, ring contraction, and atom transmutation of aryl scaffolds. This approach enables the synthesis of a diverse array of azepinones, unsaturated amides, isoquinolines, and indenones from naphthol substrates. Its application in the synthesis of bioactive and functional molecules as well as the conversion of complex molecular skeletons underscores its broad potential applicability. Mechanistic investigations suggest the intermediacy of the dearomatized intermediates.

show abstract

Rhodium(II)-Catalyzed Asymmetric Cyclopropanation and Desymmetrization of [2.2]Paracyclophanes

Ly,

Bacsa,

Davies

2024

ACS Catal.

View full text Add to dashboard Cite

Chiral [2.2]paracyclophane derivatives are of considerable interest because of their potential in asymmetric catalysis and the development of chiral materials. This study describes the scope of rhodium-catalyzed reactions of aryldiazoacetates with [2.2]paracyclophanes. The reaction with the parent [2.2]paracyclophane resulted in cyclopropanation at two positions, the ratio of which is catalyst-controlled. Because of the strain in the system, one of the cyclopropanes exists primarily as the norcaradiene structure, whereas the other preferentially exists as the cycloheptatriene conformer. In contrast, the reaction with [3.3]paracyclophane results in benzylic C−H functionalization. The reactions with substituted [2.2]paracyclophanes using chiral catalysts can result in either kinetic resolution or desymmetrization. The Rh 2 (S-p-PhTPCP)] 4 -catalyzed reaction of monosubstituted paracyclophanes results in kinetic resolution with a selectivity (s) factor of up to 20, whereas reactions on C 2v -symmetric disubstituted [2.2]paracyclophanes with Rh 2 (S-TPPTTL) 4 [TPPTTL = 2-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)-3,3-dimethylbutanoate] results in effective desymmetrization to form cycloheptatriene-incorporated paracyclophanes in 78−98% ee.

show abstract

Recent advances in transition-metal-catalyzed Büchner reaction of alkynes

Abstract: Medium-sized ring-containing organic molecules, especially the seven-membered rings, are significant structural motifs. However, such frameworks are considered as difficult structures to access owing to entropic effects and transannular interactions. Compared...

Cited by 3 publications

References 54 publications

Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes

Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes

Diversification of Naphthol Skeletons Triggered by Aminative Dearomatization

Rhodium(II)-Catalyzed Asymmetric Cyclopropanation and Desymmetrization of [2.2]Paracyclophanes

Contact Info

Product

Resources

About