Photochemical activation of the carboxyl group via n-acyl-2-thionothiazolidines

Burton, Lester P. J.; White, James D.

doi:10.1016/s0040-4039(00)77431-4

Cited by 22 publications

(8 citation statements)

References 8 publications

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“…Probably, compound 1i arises from the g-H abstraction by the excited thioamide S-atom, followed by elimination of ketene. Analogous g-H abstractions were observed in the photolysis of N-acylthiazolidine-2-thiones [5] and N-acylindoline-2-thiones [6]. The 1 : 1 adduct 7 was not formed when a benzene solution of 1a and indene 2e was irradiated under an O 2 atmosphere.…”

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confidence: 64%

“…with cycloalkenes 2a ± 2c, cyclohexa-1,4-diene (2d), and indene (2e), and heteroaromatics 3 could be understood in terms of the pathways shown in Scheme 4, which we had proposed for the photoreactions of thioamides and alkenes [2] [3] [5]. The spirocyclic amino-thietanes AT were formed initially through the regioselective [2 2] photocycloaddition of the CS bond of 1 and CC bond of 2 or 3.…”

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confidence: 99%

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Photoaddition Reactions of Benzoxazole‐2(3H)‐thiones to Cycloalkenes and Heteroaromatics

Nishio

Shiwa

Sakamoto

2003

Helvetica Chimica Acta

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Photoaddition reactions of benzoxazole-2-thiones 1 with cycloalkenes 2 and heteroaromatics 3 were examined. Irradiation of N-acylbenzoxazole-2-thiones 1a and 1b, and 3-(methoxycarbonyl)-and 3-(phenoxycarbonyl)benzoxazole-2(3H)-thiones (1f and 1h, resp.) in the presence of cycloalkenes 2a ± 2c, cyclohexa-1,4-diene (2d), and indene (2e) yielded 2-substituted benzoxazoles 4 ± 13, 18 and 19, and iminothietanes 14 ± 17, by intramolecular trapping of the acyl or MeOCO and PhOCO groups by thiolate anion of the zwitterionic intermediate I and by the phenolate anion of the zwitterionic intermediate II, respectively, derived from the spirocyclic amino-thietanes AT formed by [2 2] cycloaddition of the CS bond of 1 and CC bond of 2. Irradiation of 1 in the presence of heteroaromatics 3 gave the 2-substituted benzoxazoles 20 ± 33 exclusively. . To investigate the scope and limitation of the photocycloaddition of benzoxazole-2(3H)-thiones 1 and alkenes, we examined the photoreactions of 1 and cycloalkenes 2a ± 2c, cyclohexa-1,4-diene (2d) and indene (2e), and heteroaromatics 3, and our results are described in this paper (Schemes 1 and 2).

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confidence: 64%

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confidence: 99%

Photoaddition Reactions of Benzoxazole‐2(3H)‐thiones to Cycloalkenes and Heteroaromatics

Nishio

Shiwa

Sakamoto

2003

Helvetica Chimica Acta

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“…Relatively inert in the absence of light, irradiation promotes the transfer of the acyl group to a nucleophile (solvent), as shown in Scheme 16. [20] The reaction is compatible with a variety of side chains R, but the presence of an a-hydrogen atom is required. This observation suggested a Norrish-type II mechanism, leading to a ketene intermediate, which is then trapped by the nucleophile (Scheme 17).…”

Section: N-acylthiazolidine-2-thione Derivativesmentioning

confidence: 99%

Photoinduced acyl transfer

Débieux

Bochet

2010

J of Physical Organic Chem

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The acylation reaction occupies a central role in biochemistry and organic synthesis. On the one hand, it is by this very reaction that amino acids successively assemble to form peptides and proteins, and on the other hand it is a major synthetic method encompassing esterification, amidation, Friedel-Crafts reaction and many other processes routinely used both at the laboratory and the industrial scale. Photochemical activation is always an attractive alternative, because it is relatively mild (provided innocuous wavelengths are used), and no additional substance is added; thus no separation of the activator is necessary at the end of the process. In this paper, we briefly survey the most widely used methods of photoinduced acylations, and our own contribution to the field.

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“…z , DaR der Thiono-Schwefel im Imidazolin-2-thion [l 51 bzw. im Thiazolidin-2-thion[16] primar acyliert wird und daR eine leicht verlaufende S-N-Acylwanderung folgt, ist bekannt.…”

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Synthese und Dimroth‐Umlagerung von disubstituierten 5‐Imino‐1,2,4‐dithiazolidin‐3‐thionen (Senfölsulfiden)

Tittelbach¹

1991

J. Prakt. Chem.

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Synthesis and Dimroth Isomerization of Disubstituted 5‐Imino‐1,2,4‐dithiazolidine‐3‐thiones (Mustard Oil Sulfides). Treatment of N‐substituted dithiocarbamates with N‐substituted S‐chloroisothiocarbamoyl chlorides leads to disubstituted 5‐imino‐1,2,4‐dithiazolidine‐3‐thiones. Educts with different aromatic substituents give the diaryl derivatives 5, as expected by the reaction equation. Educts with one aromatic and one aliphatic substituent give 5‐alkylimino‐4‐aryl derivatives 10, regardless which starting component (3, 4, 7, 8) possesses the aliphatic or aromatic substituent. Educts with different aliphatic substituents (7, 8) leads to mixtures of isomeric derivatives 12, 13. Disubstituted 5‐imino‐1,2,4‐dithiazolidine‐3‐thiones with 5‐alkylimino group are able for Dimroth isomerization to 4‐substituted 2‐alkyl‐1,2,4‐thiadiazolidine‐3,5‐dithiones.

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Photochemical activation of the carboxyl group via n-acyl-2-thionothiazolidines

Cited by 22 publications

References 8 publications

Photoaddition Reactions of Benzoxazole‐2(3H)‐thiones to Cycloalkenes and Heteroaromatics

Photoaddition Reactions of Benzoxazole‐2(3H)‐thiones to Cycloalkenes and Heteroaromatics

Photoinduced acyl transfer

Synthese und Dimroth‐Umlagerung von disubstituierten 5‐Imino‐1,2,4‐dithiazolidin‐3‐thionen (Senfölsulfiden)

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