Phthalimidesulfenyl Chloride; Part VII:<sup>1</sup>Synthesis of 2-Substituted 3-Chlorobenzo[<i>b</i>]thiophenes and Related Heteroaromatics

The main methodologies for the synthesis of fused thiophenes (thienothiophenes, dithienothiophenes, and thienoacenes) and some of their oligomers and polymers are described. Such compounds are particularly important in materials chemistry. They have applications in organic light-emitting diodes (OLEDs), organic field effect transistors (OFETs), (dye-sensitized) solar cells, and electrochromic devices (ECDs).

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“…Two equivalents of AlCl 3 were used to bring about cyclizing electrophilic substitution to make 40 from 39 (Scheme 9) [27].…”

Section: Synthesis Of Thieno[32-b]thiophenesmentioning

confidence: 99%

Fused Thiophenes and Some Oligomers and Polymers Therefrom

Çınar

Öztürk

2014

Topics in Heterocyclic Chemistry

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“…Specifically, 1propenesulfenic acid (3) has been shown to be the precursor of (Z)-and (E)-propanethial S-oxides (4), the familiar lachrymatory factor of onions (9). Unsaturated sulfenic acid amides have demonstrated usefulness in synthesis (10)(11)(12).…”

Section: [Traduit Par La Rédaction]mentioning

confidence: 99%

Article

Refvik¹,

Schwan²

1998

Can. J. Chem.

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Lithium (E)-1-hexenesulfenate (5a) was treated with a number of TMS-X (TMS = trimethylsilyl) reagents to afford N,N-bis(trimethylsilyl)-(E)-1-hexenesulfenamide (7a) and (or) di((E)-1 hexenyl) disulfide (8), usually in low yield. The cleanest reactions, those from use of TMS-Cl (to afford 7a) and TMS-CN (which yields 8) were analyzed by variable temperature NMR. It was found that the low-temperature silylation reaction using TMS-Cl affords 7a and thiosulfinate 12 as initial products. Warming the mixture coerces the decomposition of 12. Treatment of 5a with TMS-CN also yields thiosulfinate 12 which is reduced to disulfide 8 as the temperature warms, possibly by action of cyanide ion. Evidence is presented that allows a confident structural assignment of the transient thiosulfinate 12, and mechanisms are suggested for the formation of 12. The study also led to the NMR observation of (E)-1-hexenesulfenate (5a).

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“…[10] Several years ago we reported an easy two-step (one-pot) procedure for the preparation of 3-chlorobenzo [b]thiophenes. [11] The method is based on the electrophilic addition of the phthalimidesulfenyl chloride PhtNSCl (Pht = Phthaloyl) to aryl-alkyl-or symmetrical diarylalkynes, to give (E)-b-chlorothiovinylphthalimides with high Markovnikov regioselectivity. These compounds under Lewis acid catalysis (AlCl 3 and BF 3 ·OEt 2 were demonstrated to be the reagents of choice) undergo an intramolecular electrophilic aromatic substitution with closure of the thiophene ring and elimination of the phthalimide residue (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

“…These compounds under Lewis acid catalysis (AlCl 3 and BF 3 ·OEt 2 were demonstrated to be the reagents of choice) undergo an intramolecular electrophilic aromatic substitution with closure of the thiophene ring and elimination of the phthalimide residue (Scheme 1). [11] In this paper, we describe an update of this methodology for the preparation of 2,3-disubstituted benzo [b]thiophenes of pharmaceutical interest exploiting the opportunities offered by some of the recent developments in organic synthesis. …”

Section: Introductionmentioning

confidence: 99%

2,3‐Disubstituted Benzo[b]thiophenes from Diarylalkynes via Electrophilic Addition‐Cyclization and Palladium‐Catalyzed Cross‐Coupling

Lamanna

Menichetti

2007

Adv Synth Catal

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Diarylalkynes are readily transformed in 3-chlorobenzo [b]thiophenes in a two-step electrophilic addition-cyclization procedure that runs highly efficiently in solution or in the solid phase. The heteroaromatic carbon-chlorine bond participates in palladium-catalyzed Suzuki-Miyaura or Buchwald-Hartwig cross-couplings to give, in a single step, 2,3-disubstituted derivatives of pharmacological relevance .

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Phthalimidesulfenyl Chloride; Part VII:¹Synthesis of 2-Substituted 3-Chlorobenzo[b]thiophenes and Related Heteroaromatics

Cited by 28 publications

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Fused Thiophenes and Some Oligomers and Polymers Therefrom

Fused Thiophenes and Some Oligomers and Polymers Therefrom

Article

2,3‐Disubstituted Benzo[b]thiophenes from Diarylalkynes via Electrophilic Addition‐Cyclization and Palladium‐Catalyzed Cross‐Coupling

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Phthalimidesulfenyl Chloride; Part VII:1Synthesis of 2-Substituted 3-Chlorobenzo[b]thiophenes and Related Heteroaromatics

Cited by 28 publications

References 0 publications

Fused Thiophenes and Some Oligomers and Polymers Therefrom

Fused Thiophenes and Some Oligomers and Polymers Therefrom

Article

2,3‐Disubstituted Benzo[b]thiophenes from Diarylalkynes via Electrophilic Addition‐Cyclization and Palladium‐Catalyzed Cross‐Coupling

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Phthalimidesulfenyl Chloride; Part VII:¹Synthesis of 2-Substituted 3-Chlorobenzo[b]thiophenes and Related Heteroaromatics