Catalytic Asymmetric [3+1]‐Cycloaddition Reaction of Ylides with Electrophilic Metallo‐enolcarbene Intermediates

Deng, Yongming; Massey, Lynée A.; Zavalij, Peter Y.; Doyle, Michael P.

doi:10.1002/anie.201704069

Cited by 68 publications

(56 citation statements)

References 53 publications

(24 reference statements)

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“…[3] Sulfur ylides (R 2 S + –C – R 2 ; e.g., 3a , Scheme 1a) have been easily prepared from their corresponding sulfonium salts (R 2 S + –CHR 2 ·X – ) under basic conditions, and they usually serve as one-carbon synthons (the ylide carbon) in cyclopropanation, epoxidation, aziridination, and other [ n +1] cycloaddition processes with release of the corresponding sulfides (R 2 S), [4] including a recently reported [3+1] cyclo-addition reaction with enoldiazoacetates. [5] …”

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confidence: 99%

Copper‐Catalyzed Formal [4+2] Cycloaddition of Enoldiazoimides with Sulfur Ylides

et al. 2018

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Enoldiazoimides, a new subclass of enoldiazo compounds, generate enol-substituted carbonyl ylides whose reactions with sulfur ylides enable an unprecedented formal [4+2] cycloaddition. The resulting multifunctionalized indolizidinones, which incorporate sulfur, are formed in good yields under mild reaction conditions. The uniqueness of this transformation stems from the role of the silyl-protected enol, since the corresponding acetyldiazoimide failed to provide any cross-products in metal-catalyzed reactions with sulfur ylides. This copper-catalyzed cycloaddition is initiated with the generation of enol-substituted carbonyl ylides and sulfur ylides from enoldiazoimides and sulfonium salts, respectively, and proceeds through stepwise six-membered ring formation, C-O and C-S bond cleavage, and silyl and acetyl group migration.

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Copper‐Catalyzed Formal [4+2] Cycloaddition of Enoldiazoimides with Sulfur Ylides

et al. 2018

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“…Subsequent 1,2‐migration of C a or C b to the electrophilic carbene carbon atom produced cyclobutenes 24 or 25 , respectively. Notably, enantioselective copper(I)‐catalyzed [3+1] cycloaddition of enoldiazoacetates was recently developed by utilizing sulfur ylides as one‐carbon‐atom synthons, thus furnishing highly enantioenriched cyclobutene derivatives …”

Section: Cyclization Reactions Of Structurally Different Diazo Compoundsmentioning

confidence: 99%

Vinyldiazo Reagents and Metal Catalysts: A Versatile Toolkit for Heterocycle and Carbocycle Construction

Cheng

Yedoyan

et al. 2018

ChemCatChem

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Over the past decade, vinyldiazo compounds have provided mild, efficient, and highly selective methods for the construction of heterocycles and carbocycles. Dinitrogen extrusion with suitable catalysts provides the carbon framework for [3+n] cycloaddition with a large variety of dipolarophiles. This minireview, covering the latest achievements in the field of metal‐catalyzed cyclization reactions with vinyldiazo reagents, focuses on reagent‐ or catalyst‐dependent chemodivergence: different vinyldiazo reagents or metal catalysts direct reactions to different cyclization pathways that give different reaction outcomes. Accordingly, metal‐catalyzed cyclization reactions of vinyldiazo compounds with nitrosoarenes, nitrones, indoles, and other diazo compounds are chosen to showcase the controllable versatility of the combination of vinyldiazo reagents and metal catalysts.

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“…100,101 The first highly stereoselective [3+1]-cycloaddition between enoldiazoacetates and sulfur ylides has recently been reported. 102 As depicted in Scheme 8, a chiral copper(I) catalyst, generated in situ from copper(I) triflate [CuOTf·Tol 1/2 ] and double-sidearmed bisoxazoline ligand 21 , facilitated dinitrogen extrusion from triisopropylsilyl (TIPS)-protected enoldiazoacetates 1 . Consecutive nucleophilic addition of sulfur ylides 19 to the vinylogous position of the resulting copper-enolcarbenes, followed by intramolecular cyclization with displacement of the thioether (R′ 2 S) and the catalyst produced enantioenriched multifunctionalized cyclobutenes 20 .…”

Section: Mecc Reactions Of Enoldiazo Compoundsmentioning

confidence: 99%

“…Notably, the first-generation Grubbs catalyst was also successfully employed as stoichiometric one-carbon component to furnish the corresponding [3+1]-cycloaddition product in 71% yield, in which case the cyclization was accomplished by presumed nucleophilic displacement of a ruthenium leaving group. 102 …”

Section: Mecc Reactions Of Enoldiazo Compoundsmentioning

confidence: 99%

“…102,122,132,152,167,168 Furthermore, the cyclopropenes, preformed from enoldiazo compounds under catalytic or thermal conditions, have proven to be effective metallo-enolcarbene precursors in several MECC reactions. 102,115,122,124,132,165,167,168 As depicted in Scheme 35, catalyst-controlled divergent outcomes are obtained from cycloaddition reactions of enoldiazoacetate 1a with Isoquinolinium methylide 40a . 132 Coordination of the Lewis basic methylide to the carbene-bound dirhodium catalyst promotes the formation of donor–acceptor cyclopropene from rhodium-enolcarbene.…”

Section: Catalyst-controlled Switchable Chemoselectivitymentioning

confidence: 99%

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Cycloaddition reactions of enoldiazo compounds

et al. 2017

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Enoldiazo esters and amides have proven to be versatile reagents for cycloaddition reactions that allow highly efficient construction of various carbocycles and heterocycles. Their versatility is exemplified by (1) [2+n]-cycloadditions (n = 3, 4) by the enol silyl ether units of enoldiazo compounds with retention of the diazo functionality to furnish α-cyclic-α-diazo compounds that are themselves subject to further transformations of the diazo functional group; (2) [3+n]-cycloadditions (n = 1–5) by metallo-enolcarbenes formed by catalytic dinitrogen extrusion from enoldiazo compounds; (3) [2+n]-cycloadditions (n = 3, 4) by donor–acceptor cyclopropenes generated in situ from enoldiazo compounds that produce cyclopropane-fused ring systems. The role of dirhodium(II) and the emergence of copper(I) catalysts are described, as are the different outcomes of reactions initiated with these catalysts. This comprehensive review on cycloaddition reactions of enoldiazo compounds, with emphasis on methodology development, mechanistic insight, and catalyst-controlled chemodivergence, aims to provide inspiration for future discoveries in the field and to catalyze the application of enoldiazo reagents by the wider synthetic community.

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Catalytic Asymmetric [3+1]‐Cycloaddition Reaction of Ylides with Electrophilic Metallo‐enolcarbene Intermediates

Cited by 68 publications

References 53 publications

Copper‐Catalyzed Formal [4+2] Cycloaddition of Enoldiazoimides with Sulfur Ylides

Copper‐Catalyzed Formal [4+2] Cycloaddition of Enoldiazoimides with Sulfur Ylides

Vinyldiazo Reagents and Metal Catalysts: A Versatile Toolkit for Heterocycle and Carbocycle Construction

Cycloaddition reactions of enoldiazo compounds

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