Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(13), P. 3239 - 3244
Published: Jan. 1, 2023
A copper-catalyzed three-component sulfonylation reaction is presented. This protocol provides easy and straightforward access to structurally diverse γ-keto aryl sulfones with good yields, mild conditions, low catalyst loading, functional group tolerance.
Language: Английский
Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(25)
Published: April 13, 2022
Stereoselective cyclopropanation reaction of alkenes is usually achieved by metal complexes via singlet-metal-carbene intermediates. However, previous transition-metal-catalyzed with acylsilanes afforded low diastereoselectivity. Herein, we report the first visible-light-induced transition-metal-free terminal trifluoroacetylsilanes and difluoroacetylsilanes. Both aromatic aliphatic as well electron-deficient are suitable substrates for highly cis-selective [2+1] cyclization reaction. A combination experimental computational studies identified triplet carbenes being key intermediates in this transformation. The gram scale late-stage functionalization demonstrated synthetic potential strategy.
Language: Английский
Citations
73
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(6), P. 3588 - 3598
Published: Feb. 3, 2023
Catalytic enantioselective functionalization of cyclobutenes constitutes a general and modular strategy for construction enantioenriched complex cyclobutanes bearing multiple stereogenic centers, as chiral four-membered rings are common motifs in biologically active molecules versatile intermediates organic synthesis. However, synthesis through such remained significantly limited. Herein, we report series unprecedented cobalt-catalyzed carbon-carbon bond forming reactions that initiated carbometalation. The protocols feature diastereo- introduction allyl, alkynyl, functionalized alkyl groups. Mechanistic studies indicated an unusual 1,3-cobalt migration subsequent β-carbon elimination cascade process occurred the allyl addition. These new discoveries established elementary cobalt catalysis extension diversity nucleophiles transformations cyclobutenes.
Language: Английский
Citations
31
Organometallics, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 16, 2025
Isomerization of cyclopropane-containing molecules offers a direct pathway to access all their diastereoisomers. Current catalytic methods, however, are largely confined isomerization carbonyl- and vinyl-substituted cyclopropanes. We report cyclopropanols, which converts readily accessible cis-1,2-disubstituted cyclopropanols into more stable, yet often less accessible, trans-isomers. This enables straightforward both diastereoisomers these small-ring molecules. Mechanistic studies indicate the reactivity silver homoenolates.
Language: Английский
Citations
1
Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(12), P. 4775 - 4781
Published: March 16, 2021
We report herein an enantioselective conjugate addition reaction of a zinc homoenolate, catalytically generated via ring opening cyclopropanol, to α,β-unsaturated ketone. The is promoted by aminoalkoxide catalyst from Et2Zn and chiral β-amino alcohol afford 1,6-diketones, which undergo, upon heating, intramolecular aldol condensation furnish highly substituted cyclopentene derivatives with good high enantioselectivities. has proved applicable various 1-substituted cyclopropanols as well chalcones related enones. amino enable ligand-accelerated catalysis the homoenolate generation its addition. Positive nonlinear effects lower reactivity racemic have been observed, can be attributed stable inactive heterochiral dimer.
Language: Английский
Citations
49
Organic Letters, Journal Year: 2022, Volume and Issue: 24(14), P. 2699 - 2704
Published: April 7, 2022
Herein, we reported a Ni-catalyzed carbonylation of cyclopropanol with benzyl bromide to afford multisubstituted cyclopentenone under 1 atm CO. The reaction proceeds through cascade bromides, followed by generation nickel homoenolate from cyclopropanols via β-C elimination 1,4-diketones, which undergoes intramolecular Aldol condensation furnish highly substituted derivatives in moderate good yields. exhibits high functional group tolerance broad substrate scope.
Language: Английский
Citations
30
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)
Published: July 25, 2023
We report here a homo-Mannich reaction of cyclopropanol with an iminium ion, generated by asymmetric allylic dearomatization indole, to construct tricyclic hydrocarbazole core, which is shared variety monoterpenoid indole alkaloids across families. Through this approach, all-carbon quaternary stereogenic center as well allyl and ketone group were installed. Using functionalized the structural platform, D ring E rings different sizes (i.e., five-, six-, seven-membered) successively or simultaneously assembled, leading collective synthesis seven belonging ibophyllidine, Aspidosperma, Kopsia, Melodinus alkaloid
Language: Английский
Citations
15
Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(19), P. 4941 - 4971
Published: Jan. 1, 2023
A summary of the various ring opening reactions strained and unstrained cycloalkanols is elaborated in present review. Key emphasis on reactivities pertaining to cyclopropanols, cyclobutanols higher analogues provided.
Language: Английский
Citations
14
Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(44), P. 18400 - 18405
Published: Oct. 29, 2021
We report herein a zinc-catalyzed β-allylation of cyclopropanols with Morita–Baylis–Hillman (MBH) carbonates retention the cyclopropane ring. The reaction is promoted by zinc aminoalkoxide catalyst, affording cyclopropyl-fused α-alkylidene-δ-valerolactone derivatives in moderate to good yields. Mechanistic experiments suggest that present does not proceed via direct β-C–H cleavage cyclopropanol, but involves homoenolate and its enolization generate key bis-nucleophilic species. α-Allylation this "enolized homoenolate" MBH carbonate would be followed regeneration ring irreversible lactonization. enolized mechanism has also been proven allow for β-functionalization alkylidenemalononitrile as partner. A sequence known cyclopropanol transformation provides an opportunity transform simple into α,β- or β,β-difunctionalized ketones.
Language: Английский
Citations
30
Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(47), P. 19975 - 19982
Published: Nov. 19, 2021
The concise, collective, and asymmetric total syntheses of four schizozygane alkaloids, which feature a "Pan lid"-like hexacyclic core scaffold bearing up to six continuous stereocenters, including two quaternary ones, are described. A new method dearomative cyclization cyclopropanol onto the indole ring at C2 was developed build ABCF system with ketone group. Another key skeleton-building reaction, Heck/carbonylative lactamization cascade, ensured rapid assembly concurrent installation an alkene By strategic use these reactions through late-stage diversifications functionalized core, first (+)-schizozygine, (+)-3-oxo-14α,15α-epoxyschizozygine, (+)-α-schizozygol synthesis (+)-strempeliopine have been accomplished in 11–12 steps from tryptamines.
Language: Английский
Citations
28
ChemistrySelect, Journal Year: 2023, Volume and Issue: 8(32)
Published: Aug. 23, 2023
Abstract Cyclopropanols, due to their particular chemistry, can participate in various synthetic reactions with retention or cleavage of the strained three‐membered ring. Direct cross‐coupling ring‐opening reaction such molecules access organic compounds, as ketones has great importance medicinal chemistry and material sciences. Hence, coupling reaction/cyclization cyclopropanols for constructing new valuable presence a transition metal catalyst under metal‐free conditions is described this context. The features are discussed, mechanisms challenging highlighted.
Language: Английский
Citations
12