Synthesis of benzannelated sultams by intramolecular Pd-catalyzed arylation of tertiary sulfonamides

Rassadin, Valentin A.; Scholz, Mirko; Klochkova, Anastasiia; Meijere, Armin de; Соколов, В. В.

doi:10.3762/bjoc.13.187

Cited by 3 publications

(6 citation statements)

References 47 publications

(36 reference statements)

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“…The Sonogashira Procedure A was followed from 2-iodo- N -(4-methoxybenzyl)aniline (100 mg, 0.29 mmol) and 8b (0.174 mL, 1.18 mmol) at 60 °C (reaction time 16 h) to afford, after purification by flash-column chromatography (silica gel; solvent A, hexane; solvent B, EtOAc; gradient from 100:0 to 80:20 A/B), 52 mg (55%) of 9a as an oil. 1 H NMR (400.16 MHz, CDCl 3 ): δ 7.30 (d, J = 8.7 Hz, 2H), 7.27 (dd, J = 7.5, 1.5 Hz, 1H), 7.12 (ddd, J = 7.7, 7.0, 1.5 Hz, 1H), 6.89 (d, J = 8.7 Hz, 2H), 6.62 (td, J = 7.5, 1.0 Hz, 1H), 6.57 (d, J = 8.1 Hz, 1H), 4.94 (t, J = 5.6 Hz, 1H), 4.34 (d, J = 5.6 Hz, 2H), 3.81 (s, 3H), 2.45 (t, J = 7.0 Hz, 2H), 1.63–1.53 (m, 2H), 1.47–1.37 (m, 2H), 1.33–1.23 (m, 4H), 0.90 (t, J = 7.0 Hz 3H) ppm.…”

Section: Methodsmentioning

confidence: 99%

“…The Sonogashira Procedure B was followed from 2-iodo- N -(4-methoxybenzyl)aniline (400 mg, 1.18 mmol) and prop-2-yn-1-yl acetate ( 8m ) (0.468 mL, 4.72 mmol) in Et 3 N (2.6 mL) (reaction time 24 h) to afford, after purification by flash-column chromatography (silica gel; solvent A, hexane; solvent B, EtOAc; gradient from 100:0 to 80:20 A/B), 170 mg (47%) of 9b as a yellow solid. Mp: 59–60 °C (hexane/EtOAc).…”

Section: Methodsmentioning

confidence: 99%

“…The Sonogashira Procedure C was followed from 2-iodo- N -(4-methoxybenzyl)aniline (500 mg, 1.47 mmol) and 8n (595 mg, 1.77 mmol) (reaction time 48 h) to afford, after purification by flash-column chromatography (C18-silica gel; solvent A, acetonitrile; solvent B, water; gradient from 70:30 to 100:0 A/B), 580 mg (72%) of 9e as a yellow oil. 1 H NMR (400.16 MHz, CDCl 3 ): δ 7.72–7.66 (m, 4H), 7.44–7.37 (m, 2H), 7.38–7.30 (m, 4H), 7.25–7.19 (m, 3H), 7.10 (ddd, J = 8.3, 7.4, 1.6 Hz, 1H), 6.83 (d, J = 8.0 Hz, 2H), 6.59 (td, J = 7.5, 1.1 Hz, 1H), 6.52 (d, J = 8.2 Hz, 1H), 4.94 (br s, 1H), 4.26 (d, J = 3.9 Hz, 2H), 3.79 (s, 3H), 3.58 (s, 2H), 1.30 (s, 6H), 1.07 (s, 9H) ppm.…”

Section: Methodsmentioning

confidence: 99%

“…The Sonogashira Procedure D was followed from 2-iodo- N -(4-methoxybenzyl)aniline (400 mg, 1.18 mmol) and triethyl(ethynyl)silane ( 8p ) (0.42 mL, 2.36 mmol) (reaction time 12 h) to afford, after purification by flash-column chromatography (silica gel, solvent A: hexane; solvent B: EtOAc; gradient from 95:5 to 90:10 A/B), 214 mg (52%) of 9k as a yellow oil. 1 H NMR (400.16 MHz, CDCl 3 ): δ 7.32 (dd, J = 7.6, 1.6 Hz, 1H), 7.29 (d, J = 8.8 Hz, 2H), 7.21–7.13 (m, 1H), 6.88 (d, J = 8.6 Hz, 2H), 6.65–6.56 (m, 2H), 4.97 (br s, 1H, NH), 4.31 (s, 2H), 3.81 (s, 3H), 0.97 (t, J = 7.9 Hz, 9H), 0.62 (q, J = 7.9 Hz, 6H) ppm.…”

Section: Methodsmentioning

confidence: 99%

“…23 N-(4-Methoxybenzyl)-2-(oct-1-yn-1-yl)aniline (9a). The Sonogashira Procedure A was followed from 2-iodo-N-(4-methoxybenzyl)aniline 109 (100 mg, 0.29 mmol) and 8b (0.174 mL, 1.18 mmol) at 60 °C (reaction time 16 h) to afford, after purification by flash-column chromatography (silica gel; solvent A, hexane; solvent B, EtOAc; gradient from 100:0 to 80:20 A/B), 52 mg (55%) of 9a as an oil. 1 H NMR (400.16 MHz, CDCl 3 ): δ 7.30 (d, J = 8.7 Hz, 2H), 7.27 (dd, J = 7.5, 1.5 Hz, 1H), 7.12 (ddd, J = 7.7, 7.0, 1.5 Hz, 1H), 6.89 ( 3-[2-(4-Methoxybenzylamino)phenyl]prop-2-yn-1-yl Acetate (9b).…”

Section: ■ Conclusionmentioning

confidence: 99%

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Palladium-Catalyzed Aminocyclization–Coupling Cascades: Preparation of Dehydrotryptophan Derivatives and Computational Study

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Dehydrotryptophan derivatives have been prepared by palladium-catalyzed aminocyclization-Heck-type coupling cascades starting from o-alkynylaniline derivatives and methyl α-aminoacrylate. Aryl, alkyl (primary, secondary, and tertiary), and alkenyl substituents have been introduced at the indole C-2 position. Further variations at the indole benzene ring, as well as the C-2-unsubstituted case, have all been demonstrated. In the case of C-2 aryl substitution, the preparation of the o-alkynylaniline substrate by Sonogashira coupling and the subsequent cyclization–coupling cascade have been performed in a one-pot protocol with a single catalyst. DFT calculations have revealed significant differences in the reaction profiles of these reactions relative to those involving methyl acrylate or methacrylate, and between the reactions of the free anilines and their corresponding carbamates. Those calculations suggest that the nature of the alkene and of the acid HX released in the HX/alkene exchange step that precedes C–C bond formation could be responsible for the experimentally observed differences in reaction efficiencies.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: ■ Conclusionmentioning

confidence: 99%

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Palladium-Catalyzed Aminocyclization–Coupling Cascades: Preparation of Dehydrotryptophan Derivatives and Computational Study

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Dual Role of Vinyl Sulfonamides as N‐Nucleophiles and Michael Acceptors in the Enantioselective Synthesis of Bicyclic δ‐Sultams

et al. 2018

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A new methodology for the synthesis of enantiomerically enriched bicyclic δ‐sultams is described, involving an initial organocatalytic intramolecular aza‐Michael reaction of vinyl sulfonamides bearing a conjugated ketone at a remote position. The resulting Michael adducts were then subjected to an intramolecular conjugate addition over the vinyl sulfone moiety, thus rendering the final bicyclic sultams containing two stereocenters. The key point of this strategy relies on the use of vinyl sulfonamides as both, nitrogen nucleophiles and Michael acceptors. The use of phosphazene‐derived bases avoided the racemization of the intermediate derivatives, rendering 6‐membered ring bicyclic δ‐sultams in enantiomerically enriched manner with a small erosion of enantiopurity. Anyway, after recrystallization, final sultams were obtained in almost enantiomerically pure form. Nevertheless, the enantioselective synthesis of either 5‐membered ring products or benzofused derivatives was found to be out of the scope of our strategy.magnified image

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Visible-Light-Promoted Radical Cyclization of N-Arylvinylsulfonamides: Synthesis of CF3/CHF2/CH2CF3-Containing 1,3-Dihydrobenzo[c]isothiazole 2,2-Dioxide Derivatives

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A photocatalyzed and highly efficient trifluoromethylation of N-arylvinylsulfonamides using commercially available CF3SO2Cl as the trifluoromethyl radical source under blue LEDs is reported. The reaction proceeds through radical cyclization under mild conditions. An investigation of the substrate scope is performed to establish a general, synthetically useful protocol for the synthesis of novel trifluoromethylated 1,3-dihydrobenzo[c]isothiazole 2,2-dioxides in moderate to high yields. This method is also successfully applied for the synthesis of difluoromethylated and trifluoroethylated 1,3-dihydrobenzo[c]isothiazole 2,2-dioxides in good to excellent yields.

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Synthesis of benzannelated sultams by intramolecular Pd-catalyzed arylation of tertiary sulfonamides

Cited by 3 publications

References 47 publications

Palladium-Catalyzed Aminocyclization–Coupling Cascades: Preparation of Dehydrotryptophan Derivatives and Computational Study

Palladium-Catalyzed Aminocyclization–Coupling Cascades: Preparation of Dehydrotryptophan Derivatives and Computational Study

Dual Role of Vinyl Sulfonamides as N‐Nucleophiles and Michael Acceptors in the Enantioselective Synthesis of Bicyclic δ‐Sultams

Visible-Light-Promoted Radical Cyclization of N-Arylvinylsulfonamides: Synthesis of CF3/CHF2/CH2CF3-Containing 1,3-Dihydrobenzo[c]isothiazole 2,2-Dioxide Derivatives

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