Rhodium-catalyzed carbene transfer to alkynes via 2-furylcarbenes generated from enynones

González, M.; López, Enol; Vicente, Rubén

doi:10.1039/c3cc47481j

Cited by 48 publications

(19 citation statements)

References 35 publications

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“…Recently, Rh(II)-catalyzed cyclopropenation of 2-furylcarbenes from enynones was reported (Scheme 30). 47 As expected, the cyclopropenes 83 can only be isolated at low temperature (0 C) and with a short reaction time (0.5-2 hr). When the reaction was conducted at a higher temperature ( form a second vinyl carbene, followed by an S E Ar reaction to give rise to different furan derivatives.…”

Section: Reactions Via Carbene Intermediatessupporting

confidence: 65%

“…(2) no slow addition of the carbene precursor required (the dimerization reaction of enynals and enynones is typically much slower). The 2-furanyl carbene generated in 5-exo-dig cyclization demonstrated various applications in carbene transfer reactions, including oxidation, 46 cyclopropanation, [31][32][33] cyclopropenation, 47 C-H insertion, 48 X-H insertion, 33,49 aziridination, 50 cross-coupling, 51,52 and so on (Scheme 27).…”

Section: Reactions Via Carbene Intermediatesmentioning

confidence: 99%

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Transition-Metal-Catalyzed Intramolecular Nucleophilic Addition of Carbonyl Groups to Alkynes

Chen

Zhu

2018

Chem

218

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Compounds consisting of a carbonyl group and an alkyne group, especially enynals and enynones, are versatile and powerful building blocks for generating structurally diverse polycyclic compounds. In the past decades, the transitionmetal-catalyzed nucleophilic addition of a carbonyl group to an alkyne has attracted great interest for the high reactivity, good selectivity, excellent functional-group tolerance, and mild reaction conditions. Most importantly, versatile intermediates, such as pyrylium-ion, metal-carbene, 1,3-dipole, and metal-vinyl species, make it highly attractive for both the development of synthetic methodologies and applications in the synthesis of bioactive compounds or complex naturally occurring skeletons. This review focuses on the transition-metal-catalyzed nucleophilic addition of carbonyl groups to alkynes with an emphasis on the scope and limitations, the mechanisms, and applications in organic synthesis.

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Section: Reactions Via Carbene Intermediatessupporting

confidence: 65%

Section: Reactions Via Carbene Intermediatesmentioning

confidence: 99%

Transition-Metal-Catalyzed Intramolecular Nucleophilic Addition of Carbonyl Groups to Alkynes

Chen

Zhu

2018

Chem

218

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“…The dienone undergoes pericyclic ring closure to afford the final product. A M a n u s c r i p t [1052]. The proposed mechanism involves the formation of a furylcarbenerhodium complex (e.g.…”

Section: Scheme 78 Group 9 Nhc Complexesmentioning

confidence: 99%

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

Herndon

2016

Coordination Chemistry Reviews

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“…As an alternative to diazo compounds as carbene precursor, Vicente et al reported the rhodiumcatalyzed cyclopropenation of alkynes using conjugated enynones as diazo surrogates. 23 Interestingly, an implementation of this strategy with the unprecedented use of zinc catalysts in cyclopropenations was also reported. 24 Indeed, inexpensive ZnCl 2 proved to have superior activity in these reactions with respect to widely used dirhodium carboxylates, including reactions with internal alkynes (Scheme 8).…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Recent Progresses towards the Strengthening of Cyclopropene Chemistry

Vicente

2016

Synthesis

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This short review focuses on the most relevant achievements in the field of cyclopropene chemistry including their syntheses, reactivities, and applications. As the chemistry of cyclopropenes has rapidly evolved in the last few years, valuable implementations on synthetic approaches are nowadays available. Moreover, exciting and useful applications by means of cyclopropenes in organic synthesis and other research areas have also been disclosed. Herein, an overview covering advances accomplished from 2011 until the beginning of 2016 is presented. 1 Introduction 2 Progress on Cyclopropene Syntheses 3 Reactivity of Cyclopropenes 3.1 Carbometalations and Related Reactions 3.2 Cycloisomerizations to Furan Derivatives and Related Reactions 3.3 Cyclopropene Isomerization to Vinyl Carbene Intermediates 3.4 Miscellanea of Reactions 4 Applications of Cyclopropenes 5 Conclusion Key words catalysis, cyclopropenes, cyclopropanes, ring strain, synthesis Rubén Vicente studied chemistry at the Complutense University in Madrid. He obtained his Ph.D. from the University of Oviedo in 2006 with Prof. J. Barluenga, developing synthetic applications of Fischer carbenes. After short research stays at the University of Bonn and Boston College, he spent three years as a Postdoctoral Researcher sponsored by the Humboldt Foundation in the group of Prof. L. Ackermann (Georg-August-Universität, Göttingen, 2007-2009), working on C-H bond functionalizations. He returned to Oviedo in 2010 within the 'Juan de la Cierva' program and since 2012 he has held a 'Ramón y Cajal' Fellowship. In 2014, he was awarded with the Young Investigator Award from the Spanish Royal Chemical Society. His interests include the discovery of new reactivity patterns and sustainable catalysis.

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Rhodium-catalyzed carbene transfer to alkynes via 2-furylcarbenes generated from enynones

Abstract: A rhodium-catalyzed carbene transfer to alkynes is reported. Easily available enynones served as the carbene source replacing diazocompounds. The overall process involved a cyclization-cyclopropenation-ring enlargement sequence.

Cited by 48 publications

References 35 publications

Transition-Metal-Catalyzed Intramolecular Nucleophilic Addition of Carbonyl Groups to Alkynes

Transition-Metal-Catalyzed Intramolecular Nucleophilic Addition of Carbonyl Groups to Alkynes

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

Recent Progresses towards the Strengthening of Cyclopropene Chemistry

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