Ruthenium Catalyzed Rearrangement of Ene-cyclopropenes. Divergent Reaction Pathways

López‐Rodríguez, Alberto; Domı́nguez, Gema; Pérez‐Castells, Javier

doi:10.1021/acs.joc.8b02849

Cited by 24 publications

(17 citation statements)

References 61 publications

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“…As part of a study investigating the ruthenium-catalyzed reactions of 1,6-cyclopropene-enes, Peŕez-Castells and coworkers briefly compared the reaction of these systems with AuCl and AuCl 3 . 110 The 1,6-cyclopropene-enes 373 were structurally distinct from the Cossy and Meyer system, bearing a C3 ester group in place of a gem-dimethyl group (Scheme 65). However, gold-catalyzed ring-opening occurred in a similar manner to provide gold carbenoid 375 that partakes in intramolecular cyclopropanation to yield bicycle[4.1.0] derivatives 377 in good yield and as a single diastereoisomer via transition state 376.…”

Section: Gold-catalyzed Ring-opening Cyclopropanation Reactionsmentioning

confidence: 94%

Gold-Catalyzed Conversion of Highly Strained Compounds

et al. 2020

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The past decade has witnessed the golden age of homogeneous gold-catalyzed reactions, especially those that involve the transformation of highly strained molecules into complex molecular architectures. Gold catalysts, with unique electronic properties and catalytic abilities, have elevated versatile reaction modes through π-interaction induced activation. On the basis of increasing research interest in this topic, together with the significant development of various ligands, including phosphine ligands and azacyclic or noncyclic carbene ligands, the understanding of the catalytic function of gold catalysts has become much deeper and more comprehensive. Different reaction needs thus could be adapted by a novel gold catalyst with a diversified ligand selection. Furthermore, the whole evolution of the gold catalysis on synthetic methodologies has realized and expanded its application into natural product synthesis as well as the potentiality of drug discovery, which endows this ancient metal with a magnificent renaissance. The reactivity of strained small ring molecules with high tension has always been an important research topic in organic chemistry. When the highly strained small ring is linked with a π-electron rich moiety or contains a heteroatom, the gold activation of the π-system or coordination with the heteroatom can initiate a cascade reaction, usually followed by ring opening or expansion. These processes can result in the rapid construction of complex and distinct molecular structures, many of which feature in biologically important molecules. In this review, we will mainly summarize the advances on diverse reaction types and molecular constructions accomplished by homogeneous gold catalysis using highly strained substrates, including methylenecyclopropanes (MCPs), vinylidenecyclopropanes (VDCPs), cyclopropenes as well as aziridine- and epoxide-containing molecules, focusing on the last 10 years. For functionalized alkynyl cyclopropanes, several early inspiring and elegant examples will be described in this review for systematically understanding these transformations.

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Section: Gold-catalyzed Ring-opening Cyclopropanation Reactionsmentioning

confidence: 94%

Gold-Catalyzed Conversion of Highly Strained Compounds

et al. 2020

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“…More interestingly, Pérez-Castells and co-workers described a regiodivergent reactivity with 1,6-cyclopropene-enes 13 decorated with an ester group when using AuCl or Cp*RuCl(cod) as catalysts (Scheme B) . While gold-catalyst followed the expected pathway, Ru-catalyst operated with reversed regioselectivity during the cyclopropene cleavage generating a different vinyl carbene intermediate.…”

Section: Metal-mediated Ring-opening Reactions Of Cyclopropenes Invol...mentioning

confidence: 99%

“…57 More recently, Peŕez-Castells and co-workers observed high yielding dimerizations of 1,n-cyclopropene-enes 88, which occurred when intramolecular cyclopropanations were not a favorable reaction pathway (Scheme 15C). 54 The cross-coupling reaction between two different carbenes to prepare nonsymmetric alkenes is a more interesting reaction from a synthetic standpoint. However, control of the selectivity in this process is extremely challenging due to the competence of the homocoupling reaction.…”

Section: Cyclopropenes In Carbene−carbene Coupling Reactionsmentioning

confidence: 99%

“…First, Woo and co-workers described a gold nanoparticles-catalyzed dimerization of 3,3-diphenylcyclopropene ( 20 ) (Scheme B) . More recently, Pérez-Castells and co-workers observed high yielding dimerizations of 1, n -cyclopropene-enes 88 , which occurred when intramolecular cyclopropanations were not a favorable reaction pathway (Scheme C) …”

Section: Metal-mediated Ring-opening Reactions Of Cyclopropenes Invol...mentioning

confidence: 99%

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C–C Bond Cleavages of Cyclopropenes: Operating for Selective Ring-Opening Reactions

Vicente

2020

Chem. Rev.

139

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This review highlights key reactivities relying on C–C bond cleavages of cyclopropenes. Metal-catalyzed and metal-free transformations are covered in reactions involving direct ring-opening processes or transformations through nonisolable cyclopropane intermediates generated from cyclopropenes. Special emphasis is on the synthetic utility and mechanistic aspects of methodologies discussed along the revision. Different types of reactivities are covered in separate sections including generation of vinyl carbenes and their reactions, metathesis processes, heterocycles syntheses, SEAr reactions, metalation-ring opening sequences, cycloadditions involving ring-cleavages or rearrangements. The focus is on results described from 2007 to the end of 2019, yet relevant pioneering transformations are eventually included.

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“…[6][7][8][9][10] Cyclopropenes have been demonstrated to be unique vinyl carbene precursors [11][12][13] with the advantages of low toxicity and explosive nature compared to N-tosylhydrazones and diazo compounds, [14][15][16] though they are rarely exploited in intermolecular cyclopropanation with functionalized alkenes. [17][18][19][20][21] It is difficult to regulate and control the geometry of the newly formed C-C double bond after the ring-opening of unsymmetrical 3,3-disubsubstituted cyclopropenes. [22][23][24][25][26][27] Lee and Vicente successively developed gold and zinc catalyzed cyclopropanation of alkenes, although both exhibited low E/Z and syn/anti stereoselectivities (Fig.…”

Section: Introductionmentioning

confidence: 99%