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Search for "carbon–carbon bond cleavage" in Full Text gives 4 result(s) in Beilstein Journal of Organic Chemistry.
Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds
- Alemayehu Gashaw Woldegiorgis and
- Xufeng Lin
Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185
- chiral N-arylbenzimidazoles involving a carbon–carbon bond cleavage under optimal reaction conditions. In the presence of CPA 2, N1-(aryl)benzene-1,2-diamines 66 were used in the reaction with multicarbonyl compounds 67 and 68 and afforded the corresponding products, axially chiral N-arylbenzimidazoles
Graphical Abstract
Figure 1: Representative examples of axially chiral biaryls, heterobiaryls, spiranes and allenes as ligands a...
Figure 2: Selected examples of axially chiral drugs and bioactive molecules.
Figure 3: Axially chiral functional materials and supramolecules.
Figure 4: Important chiral phosphoric acid scaffolds used in this review.
Scheme 1: Atroposelective aryl–aryl-bond formation by employing a facile [3,3]-sigmatropic rearrangement.
Scheme 2: Atroposelective synthesis of axially chiral biaryl amino alcohols 5.
Scheme 3: The enantioselective reaction of quinone and 2-naphthol derivatives.
Scheme 4: Enantioselective synthesis of multisubstituted biaryls.
Scheme 5: Enantioselective synthesis of axially chiral quinoline-derived biaryl atropisomers mediated by chir...
Scheme 6: Pd-Catalyzed atroposelective C–H olefination of biarylamines.
Scheme 7: Palladium-catalyzed directed atroposelective C–H allylation.
Scheme 8: Enantioselective synthesis of axially chiral (a) aryl indoles and (b) biaryldiols.
Scheme 9: Asymmetric arylation of indoles enabled by azo groups.
Scheme 10: Proposed mechanism for the asymmetric arylation of indoles.
Scheme 11: Enantioselective synthesis of axially chiral N-arylindoles [38].
Scheme 12: Enantioselective [3 + 2] formal cycloaddition and central-to-axial chirality conversion.
Scheme 13: Organocatalytic atroposelective arene functionalization of nitrosonaphthalene with indoles.
Scheme 14: Proposed reaction mechanism for the atroposelective arene functionalization of nitrosonaphthalenes.
Scheme 15: Asymmetric construction of axially chiral naphthylindoles [65].
Scheme 16: Enantioselective synthesis of axially chiral 3,3’-bisindoles [66].
Scheme 17: Atroposelective synthesis of 3,3’-bisiindoles bearing axial and central chirality.
Scheme 18: Enantioselective synthesis of axially chiral 3,3’-bisindoles bearing single axial chirality.
Scheme 19: Enantioselective reaction of azonaphthalenes with various pyrazolones.
Scheme 20: Enantioselective and atroposelective synthesis of axially chiral N-arylcarbazoles [73].
Scheme 21: Atroposelective cyclodehydration reaction.
Scheme 22: Atroposelective construction of axially chiral N-arylbenzimidazoles [78].
Scheme 23: Proposed reaction mechanism for the atroposelective synthesis of axially chiral N-arylbenzimidazole...
Scheme 24: Atroposelective synthesis of axially chiral arylpyrroles [21].
Scheme 25: Synthesis of axially chiral arylquinazolinones and its reaction pathway [35].
Scheme 26: Synthesis of axially chiral aryquinoline by Friedländer heteroannulation reaction and its proposed...
Scheme 27: Povarov cycloaddition–oxidative chirality conversion process.
Scheme 28: Atroposelective synthesis of oxindole-based axially chiral styrenes via kinetic resolution.
Scheme 29: Synthesis of axially chiral alkene-indole frame works [45].
Scheme 30: Proposed reaction mechanism for axially chiral alkene-indoles.
Scheme 31: Atroposelective C–H aminations of N-aryl-2-naphthylamines with azodicarboxylates.
Scheme 32: Synthesis of brominated atropisomeric N-arylquinoids.
Scheme 33: The enantioselective syntheses of axially chiral SPINOL derivatives.
Scheme 34: γ-Addition reaction of various 2,3-disubstituted indoles to β,γ-alkynyl-α-imino esters.
Scheme 35: Regio- and stereoselective γ-addition reactions of isoxazol-5(4H)-ones to β,γ-alkynyl-α-imino ester...
Scheme 36: Synthesis of chiral tetrasubstituted allenes and naphthopyrans.
Scheme 37: Asymmetric remote 1,8-conjugate additions of thiazolones and azlactones to propargyl alcohols.
Scheme 38: Synthesis of chiral allenes from 1-substituted 2-naphthols [107].
Carbon–carbon bond cleavage for Cu-mediated aromatic trifluoromethylations and pentafluoroethylations
- Tsuyuka Sugiishi,
- Hideki Amii,
- Kohsuke Aikawa and
- Koichi Mikami
Beilstein J. Org. Chem. 2015, 11, 2661–2670, doi:10.3762/bjoc.11.286
- -okayama, Meguro-ku, Tokyo 152-8552, Japan 10.3762/bjoc.11.286 Abstract This short review highlights the copper-mediated fluoroalkylation using perfluoroalkylated carboxylic acid derivatives. Carbon–carbon bond cleavage of perfluoroalkylated carboxylic acid derivatives takes place in fluoroalkylation
- fluoroalkylated aromatics. Keywords: β-carbon elimination; carbon–carbon bond cleavage; decarboxylation; tetrahedral intermediate; trifluoroacetate; fluoral; trifluoromethylation; Introduction Organofluorine compounds attract attention because of their applicability in various fields, such as medicine
- hemiaminals derived from fluoral (CF3C(OSiMe3)NR2), can generate CnF2n+1Cu via carbon–carbon bond cleavage. Herein we focus on Cu-mediated perfluoroalkylation reactions through which carbon dioxide, the esters, or the N-formylamines are eliminated from the perfluoroalkyl reagents. Review Decarboxylation of
Graphical Abstract
Scheme 1: Trifluoromethylation using trifluoroacetate.
Scheme 2: Decarboxylative pentafluoroethylation and its application.
Scheme 3: Trifluoromethyation with trifluoroacetate in a flow system.
Scheme 4: Trifluoromethylation of 4-bromotoluene by [(NHC)Cu(TFA)].
Scheme 5: Trifluoromethylation of aryl iodides with small amounts of Cu and Ag2O. aThe yield was determined b...
Scheme 6: C–H trifluoromethylation of arenes using trifluoroacetic acid.
Scheme 7: CF3Cu generated from chlorofluoroacetate and CuI.
Scheme 8: [18F]Trifluoromethyation with difluorocarbenes for PET. aRadiochemical yield determined by HPLC.
Scheme 9: Trifluoromethylation with trifluoroacetate and copper iodide.
Scheme 10: Preparation of trifluoromethylcopper from trifluoromethyl ketone.
Scheme 11: Trifluoromethylation of aryl iodides. aIsolated yield. b1 equivalent each of CF3Cu reagent and 1,10...
Scheme 12: Pentafluoroethylation of aryl bromides. aYield was determined by 19F NMR analysis using benzotriflu...
Scheme 13: Perfluoroalkylation reactions of arylboronic acids. aIsolated yield. bDMF was used instead of tolue...
Scheme 14: Trifluoromethylation with silylated hemiaminal of fluoral.
Scheme 15: Catalytic trifluoromethylation with a fluoral derivative.
Scheme 16: The scope of Cu-catalyzed aromatic trifluoromethylation. The yield was determined by 19F NMR analys...
Scheme 17: Plausible mechanism of Cu-catalyzed aromatic trifluoromethylation [53].
Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation
- Kei Murakami and
- Hideki Yorimitsu
Beilstein J. Org. Chem. 2013, 9, 278–302, doi:10.3762/bjoc.9.34
- carbozincation of oxabicycloalkenes [94]. Terao and Kambe reported two types of intriguing ring-opening carbomagnesiations of a methylenecyclopropane that proceed through site-selective carbon–carbon bond cleavage (Scheme 24) [95]. The reaction pathways depended on the reagents used, i.e., the reaction with a
- phenylmagnesium reagent provided 3i whereas the reaction with a vinylmagnesium reagent gave 3j. The reaction mechanisms are shown in Scheme 25. They proposed that the carbon–carbon bond cleavage happened prior to the carbometalation reactions, which is different from other ring-opening reactions of cyclopropenes
- [96][97] where carbometalation is followed by carbon–carbon bond cleavage. Firstly, the oxidative addition of methylenecyclopropane to the reduced nickel(0) may yield 3A or 3C. The subsequent isomerization would proceed to form 3B or 3D, respectively, and then reductive elimination would afford the
Graphical Abstract
Scheme 1: Variation of substrates for carbomagnesiation and carbozincation in this article.
Scheme 2: Copper-catalyzed arylmagnesiation and allylmagnesiation of alkynyl sulfone.
Scheme 3: Copper-catalyzed four-component reaction of alkynyl sulfoxide with alkylzinc reagent, diiodomethane...
Scheme 4: Rhodium-catalyzed reaction of aryl alkynyl ketones with arylzinc reagents.
Scheme 5: Allylmagnesiation of propargyl alcohol, which provides the anti-addition product.
Scheme 6: Negishi’s total synthesis of (Z)-γ-bisabolene by allylmagnesiation.
Scheme 7: Iron-catalyzed syn-carbomagnesiation of propargylic or homopropargylic alcohol.
Scheme 8: Mechanism of iron-catalyzed carbomagnesiation.
Scheme 9: Regio- and stereoselective manganese-catalyzed allylmagnesiation.
Scheme 10: Vinylation and alkylation of arylacetylene-bearing hydroxy group.
Scheme 11: Arylmagnesiation of (2-pyridyl)silyl-substituted alkynes.
Scheme 12: Synthesis of tamoxifen from 2g.
Scheme 13: Controlling regioselectivity of carbocupration by attaching directing groups.
Scheme 14: Rhodium-catalyzed carbozincation of ynamides.
Scheme 15: Synthesis of 4-pentenenitriles through carbometalation followed by aza-Claisen rearrangement.
Scheme 16: Uncatalyzed carbomagnesiation of cyclopropenes.
Scheme 17: Iron-catalyzed carbometalation of cyclopropenes.
Scheme 18: Enantioselective carbozincation of cyclopropenes.
Scheme 19: Copper-catalyzed facially selective carbomagnesiation.
Scheme 20: Arylmagnesiation of cyclopropenes.
Scheme 21: Enantioselective methylmagnesiation of cyclopropenes without catalyst.
Scheme 22: Copper-catalyzed carbozincation.
Scheme 23: Enantioselective ethylzincation of cyclopropenes.
Scheme 24: Nickel-catalyzed ring-opening aryl- and alkenylmagnesiation of a methylenecyclopropane.
Scheme 25: Reaction mechanism.
Scheme 26: Nickel-catalyzed carbomagnesiation of arylacetylene and dialkylacetylene.
Scheme 27: Nickel-catalyzed carbozincation of arylacetylenes and its application to the synthesis of tamoxifen....
Scheme 28: Bristol-Myers Squibb’s nickel-catalyzed phenylzincation.
Scheme 29: Iron/NHC-catalyzed arylmagnesiation of aryl(alkyl)acetylene.
Scheme 30: Iron/copper-cocatalyzed alkylmagnesiation of aryl(alkyl)acetylenes.
Scheme 31: Iron-catalyzed hydrometalation.
Scheme 32: Iron/copper-cocatalyzed arylmagnesiation of dialkylacetylenes.
Scheme 33: Chromium-catalyzed arylmagnesiation of alkynes.
Scheme 34: Cobalt-catalyzed arylzincation of alkynes.
Scheme 35: Cobalt-catalyzed formation of arylzinc reagents and subsequent arylzincation of alkynes.
Scheme 36: Cobalt-catalyzed benzylzincation of dialkylacetylene and aryl(alkyl)acetylenes.
Scheme 37: Synthesis of estrogen receptor antagonist.
Scheme 38: Cobalt-catalyzed allylzincation of aryl-substituted alkynes.
Scheme 39: Silver-catalyzed alkylmagnesiation of terminal alkyne.
Scheme 40: Proposed mechanism of silver-catalyzed alkylmagnesiation.
Scheme 41: Zirconium-catalyzed ethylzincation of terminal alkenes.
Scheme 42: Zirconium-catalyzed alkylmagnesiation.
Scheme 43: Titanium-catalyzed carbomagnesiation.
Scheme 44: Three-component coupling reaction.
Scheme 45: Iron-catalyzed arylzincation reaction of oxabicyclic alkenes.
Scheme 46: Reaction of allenyl ketones with organomagnesium reagent.
Scheme 47: Regio- and stereoselective reaction of a 2,3-allenoate.
Scheme 48: Three-component coupling reaction of 1,2-allenoate, organozinc reagent, and ketone.
Scheme 49: Proposed mechanism for a rhodium-catalyzed arylzincation of allenes.
Scheme 50: Synthesis of skipped polyenes by iterative arylzincation/allenylation reaction.
Scheme 51: Synthesis of 1,4-diorganomagnesium compound from 1,2-dienes.
Scheme 52: Synthesis of tricyclic compounds.
Scheme 53: Manganese-catalyzed allylmagnesiation of allenes.
Scheme 54: Copper-catalyzed alkylmagnesiation of 1,3-dienes and 1,3-enynes.
Scheme 55: Chromium-catalyzed methallylmagnesiation of 1,6-diynes.
Scheme 56: Chromium-catalyzed allylmagnesiation of 1,6-enynes.
Scheme 57: Proposed mechanism of the chromium-catalyzed methallylmagnesiation.
Organic synthesis using (diacetoxyiodo)benzene (DIB): Unexpected and novel oxidation of 3-oxo-butanamides to 2,2-dihalo-N-phenylacetamides
- Wei-Bing Liu,
- Cui Chen,
- Qing Zhang and
- Zhi-Bo Zhu
Beilstein J. Org. Chem. 2012, 8, 344–348, doi:10.3762/bjoc.8.38
- carbonyl carbon atom affords intermediate 7. A subsequent carbon–carbon bond cleavage of the labile α,α-dichloro β-keto amide through a retro-Claisen condensation reaction [41] generates intermediate 8. Finally, the electrophilic attack of a proton on the carbon–carbon double bond resulted in the final
Graphical Abstract
Scheme 1: Synthesis of 1-carbamoyl-2-oxopropyl acetates.
Scheme 2: Synthesis of 2,2-dihalo-N-phenylacetamides.
Scheme 3: Synthesis of dichloroacetamides. Reagents and conditions: 1 (1.0 mmol), dioxane (2 mL), DIB (1.3 eq...
Scheme 4: Synthesis of dibromoacetamides. Reagents and conditions: 1 (1.0 mmol), dioxane (2 mL), DIB (1.3 equ...
Scheme 5: Probe the mechanism.
Scheme 6: Tentative mechanism for the synthesis of 2,2-dihalo-N-phenylacetamides.
