Copper(I)‐Catalyzed One‐Pot Synthesis of 2‐Iminobenzo‐ 1,3‐oxathioles from <i>ortho</i>‐Iodophenols and Isothiocyanates

Lv, Xin; Liu, Yunyun; Qian, Weixing; Wang, Bao

doi:10.1002/adsc.200800461

Cited by 53 publications

(23 citation statements)

References 37 publications

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“…It is known that for heteroarylations, iodoarenes having a strong electron-donating group react more slowly as compared to substrates possessing an electron-withdrawing group. [9] Perhaps a highly active species is formed by the oxidative addition of iodonitroarenes (d) and (e) as shown in Scheme 4. This active species could undergo nucleophilic substitution either with the soft sulfur nucleophile (path I) or with the hard amine nucleophile (path II) giving S-arylated cyanamides and N-aryl-2-aminobenzothiazole, respectively.…”

Section: Resultsmentioning

confidence: 98%

Copper(I)‐Catalyzed Cascade Synthesis of 2‐Arylsulfanyl‐ arylcyanamides

et al. 2010

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Abstract:We have developed a ligand-assisted copper(I)-catalyzed two sequential heteroarylation sequence. An intramolecular S-arylation is followed by an intermolecular N-arylation leading to the direct synthesis of N-aryl-2-aminobenzothiazoles. In most cases however, the 2-arylsulfanyl-arylcyanamide was the major product obtained via an intramolecular C À S bond formation, associated with C À S bond breakage, followed by an intermolecular S-arylation. The selectivity of this ligand-assisted reaction is quite different as compared to that of ligand-free reactions and the rates are much faster giving good yields of products. Various cyanamides can be prepared in excellent yields from their corresponding 1-substituted thioureas with or without the assistance of a ligand with a catalytic quantity of copper(I).

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Section: Resultsmentioning

confidence: 98%

Copper(I)‐Catalyzed Cascade Synthesis of 2‐Arylsulfanyl‐ arylcyanamides

et al. 2010

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“…There are only a few reports concerning the synthesis of this valuable motif, either by [4+1] cycloaddition reactions employing harsh conditions (100ºC, sealed tube) in argon atmosphere 23 or by Cu(I)-catalysed coupling of o-iodophenols and aryl isothiocyanates under nitrogen atmosphere at 80ºC. 24 The 2-imino-1,3-oxathiolane core is present in compounds with potential bioactivities. 23,25 With this in mind, we designed a strategy where by simple reduction of the carbonyl moiety plus further addition of a suitable base and/or adjuvant such as crown ether or phase transfer catalyst, 21 it would be possible to obtain the desired heterocycle.…”

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confidence: 99%

Simple and quick preparation of α-thiocyanate ketones in hydroalcoholic media. Access to 5-aryl-2-imino-1,3-oxathiolanes

et al. 2009

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Simple and quick preparation of α-thiocyanate ketones in hydroalcoholic media. Access to 5-aryl-2-imino-1,3-oxathiolanes A simple preparation on gram-scale of thiocyanate derivatives via nucleophilic substitution of halogenated compounds with SCN salts at high substrate concentrations in a few minutes and excellent yields was successfully accomplished in hydroalcoholic media. The obtained compounds were employed for the efficient synthesis of valuable 5-aryl-2-imino-1,3-oxathiolane derivatives (a one-pot approach is also presented).In the last few years, sustainable processes are highly demanded in the chemical industry.1 The "process efficiency"concept is not only related to a high chemical yield, but also to the minimised use of large amounts of harmful organic solvents and production of chemical waste. have been shown. Finally, the formation of β-hydroxy thiocyanates via oxirane ring-opening with NH 4 SCN has been described. 21 In most cases, several reagents, organic solvents and high temperatures were employed, and therefore purification by chromatography was necessary. This is in contrast with the optimum conditions to synthesise these compounds since the isomerisation thiocyanate-isothiocyanate can occur in solution at temperatures above 50ºC and/or acidic conditions. 10,16,22 For these reasons, the development of new procedures for the easy and rapid synthesis of thiocyanate derivatives in high yields is required. Herein we report our efforts in the preparation of versatile thiocyanate compounds in aqueous mixtures at high substrate concentrations and further conversion into the interesting heterocyclic 2-imino-1,3-oxathiolane system employing mild reaction conditions and cheap reagents.

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“…It enables the assembly of various 2H-1,4-benzoxazin-3-(4H)-ones in good to excellent yields from a variety of 2-(o-haloaryloxy)acyl chlorides and primary amines.. Comparing with the previous reported one-pot methods, 9 this method could directly and conveniently introduce various substituents on the 4-position of the products (by simply varying the starting amines). As little as 5 mol% of the Cu(I)-catalyst worked well.…”

Section: Discussionmentioning

confidence: 98%

Copper-catalyzed one-pot synthesis of 2H-1,4-benzoxazin-3-(4H)-ones from 2-(o-haloaryloxy)acyl chlorides and primary amines

Hu¹,

Xia²,

Zheng³

et al. 2012

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A facile and efficient Cu(I)-catalyzed one-pot synthesis of 2H-1,4-benzoxazin-3-(4H)-one derivatives has been developed. The condensation between 2-(o-haloaryloxy)acyl chlorides and primary amines followed by Cu(I)-catalyzed intramolecular C-N bond coupling afforded a variety of 2H-1,4-benzoxazin-3-(4H)-ones in good to excellent yields. Diversified substitutents on the 4-position could be conveniently introduced.

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Copper(I)‐Catalyzed One‐Pot Synthesis of 2‐Iminobenzo‐ 1,3‐oxathioles from ortho‐Iodophenols and Isothiocyanates

Cited by 53 publications

References 37 publications

Copper(I)‐Catalyzed Cascade Synthesis of 2‐Arylsulfanyl‐ arylcyanamides

Copper(I)‐Catalyzed Cascade Synthesis of 2‐Arylsulfanyl‐ arylcyanamides

Simple and quick preparation of α-thiocyanate ketones in hydroalcoholic media. Access to 5-aryl-2-imino-1,3-oxathiolanes

Copper-catalyzed one-pot synthesis of 2H-1,4-benzoxazin-3-(4H)-ones from 2-(o-haloaryloxy)acyl chlorides and primary amines

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