Synthesis of 5-Substituted Indole Derivatives. Part 4: Naratriptan from α-Anilinoacetaldehyde Dimethylacetal by TiCl4-Mediated Cyclisation

Pete, Béla; Simig, Gyula; Poszávácz, László; Tőke, Lásʐló

doi:10.3987/com-03-9838

Cited by 13 publications

(10 citation statements)

References 15 publications

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“…Previous syntheses using a Heck reaction start from 5‐bromoindole, which is either first transformed at C‐3 through electrophilic substitution and then coupled at C‐5 with a vinylsulfonamide, or vice versa , . Töke and coworkers have developed a naratriptan synthesis that proceeds via C‐5‐substituted indole 29b , which was synthesized by olefination of para ‐nitrobenzaldehyde with a methanesulfonamide, conversion to an α‐anilinoacetaldehyde diacetal, and cyclization to the indole . We have applied the Matsuda–Heck protocol developed in this work to the synthesis of Töke's naratriptan intermediate 29b (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Styrylsulfonates and ‐Sulfonamides through Pd‐Catalysed Matsuda–Heck Reactions of Vinylsulfonic Acid Derivatives and Arenediazonium Salts

2016

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Arene diazonium salts undergo Matsuda-Heck reactions with vinylsulfonates and -sulfonamides to give styrylsulfonic acid derivatives in high to excellent yields and with high to excellent selectivities. By quantifying the evolution of nitrogen over time in a gas-meter apparatus, the reactivities of ethylvinylsulfonate and the benchmark olefin methyl acrylate were compared for an electron-rich and an -deficient arene diazonium salt. Tertiary sulfonamides react in Matsuda-Heck couplings with high conversions, but require long reaction

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Section: Resultsmentioning

confidence: 99%

Styrylsulfonates and ‐Sulfonamides through Pd‐Catalysed Matsuda–Heck Reactions of Vinylsulfonic Acid Derivatives and Arenediazonium Salts

2016

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“…We hypothesized that these new compounds might be selectively modified on either electrophilic site under defined conditions. Previously, Pete and co‐workers reported that β‐arylethenesulfonyl chlorides (ArCH=CH‐SO 2 Cl) reacted with secondary amines to give sulfonamides (ArCH=CH‐SO 2 NR 2 ) in high yield . In sharp contrast, we observed that β‐phenylethenesulfonyl fluorides, like their reactive precursor, ESF, possess a strong preference for Michael addition over substitution at the sulfur center (Table ).…”

Section: Methodsmentioning

confidence: 61%

A Heck–Matsuda Process for the Synthesis of β‐Arylethenesulfonyl Fluorides: Selectively Addressable Bis‐electrophiles for SuFEx Click Chemistry

et al. 2016

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AH eck-Matsuda process for the synthesis of the otherwise difficult to access compounds, b-arylethenesulfonyl fluorides,i sd escribed. Ethenesulfonyl fluoride (i.e., vinylsulfonyl fluoride,o rE SF) undergoes b-arylation with stable and readily prepared arenediazonium tetrafluoroborates in the presence of the catalyst palladium(II) acetate to affordt he Eisomer sulfonyl analogues of cinnamoyl fluoride in 43-97 % yield. The b-arylethenesulfonyl fluorides are found to be selectively addressable bis-electrophiles for sulfur(VI) fluoride exchange (SuFEx) clickc hemistry,inwhich either the alkenyl moiety or the sulfonyl fluoride group can be the exclusive site of nucleophilic attack under defined conditions,m aking these rather simple cores attractive for covalent drug discovery.

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“…Previously, Pete and co-workers reported that β-arylethenesulfonyl chlorides (ArCH=CH–SO 2 Cl) reacted with secondary amines to give sulfonamides (ArCH=CH–SO 2 NR 2 ) in high yield. [22] In sharp contrast, we observed that β-phenylethenesulfonyl fluorides, like their reactive precursor, ESF, possess a strong preference for Michael addition over substitution at the sulfur center (Table 2). They react with cyclic secondary amines, including piperazine ( 4a , d , e ), morpholine ( 4b ), and azetidine ( 4c ) via this route, resulting in excellent yields of Michael adducts [ (±)-5 ].…”

mentioning

confidence: 83%

A Heck–Matsuda Process for the Synthesis of β‐Arylethenesulfonyl Fluorides: Selectively Addressable Bis‐electrophiles for SuFEx Click Chemistry

et al. 2016

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A Heck-Matsuda process for the synthesis of the otherwise difficult to access compounds, β-arylethenesulfonyl fluorides, is described. Ethenesulfonyl fluoride (i.e., vinylsulfonyl fluoride, or ESF) undergoes β-arylation with stable and readily prepared arenediazonium tetrafluoroborates in the presence of the catalyst palladium(II) acetate to afford the E-isomer sulfonyl analogues of cinnamoyl fluoride in 43–97% yield. The β-arylethenesulfonyl fluorides are found to be selectively addressable bis-electrophiles for sulfur(VI) fluoride exchange (SuFEx) click chemistry, in which either the alkenyl moiety or the sulfonyl fluoride group can be the exclusive site of nucleophilic attack under defined conditions, making these rather simple cores attractive for covalent drug discovery.

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Synthesis of 5-Substituted Indole Derivatives. Part 4: Naratriptan from α-Anilinoacetaldehyde Dimethylacetal by TiCl4-Mediated Cyclisation

Cited by 13 publications

References 15 publications

Styrylsulfonates and ‐Sulfonamides through Pd‐Catalysed Matsuda–Heck Reactions of Vinylsulfonic Acid Derivatives and Arenediazonium Salts

Styrylsulfonates and ‐Sulfonamides through Pd‐Catalysed Matsuda–Heck Reactions of Vinylsulfonic Acid Derivatives and Arenediazonium Salts

A Heck–Matsuda Process for the Synthesis of β‐Arylethenesulfonyl Fluorides: Selectively Addressable Bis‐electrophiles for SuFEx Click Chemistry

A Heck–Matsuda Process for the Synthesis of β‐Arylethenesulfonyl Fluorides: Selectively Addressable Bis‐electrophiles for SuFEx Click Chemistry

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