TfOH-Catalyzed Regioselective S–H Insertion of Cyclic Thioamide Derivatives with Diazo Compounds at Room Temperature

Li, Chunyan; Wang, Rui; Chen, Jiale; Jin, Jingru; Yan, Qiongjiao; Wang, Wei; Wang, Haifeng; Chen, Fen‐Er

doi:10.1021/acs.joc.2c03074

Cited by 8 publications

(1 citation statement)

References 64 publications

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“…Based on the above experiment and previous literature, a plausible catalytic cycle is outlined in Scheme . The reaction is initiated by protonation of diazoketone from TfOH to give the formation of the ionic intermediate I , which would further react with the trifluoromethylsulfonyl anion to generate the active key intermediate 4 along with the release of N 2 .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 2,4-Disubstituted Oxazoles and Thiazoles via Brønsted Acid-Catalyzed Cyclization of α-diazoketones with Amides

Luo,

Li,

Chen

et al. 2024

J. Org. Chem.

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A novel method is described for the synthesis of 2,4-disubstituted oxazole and thiazole derivates via the coupling of αdiazoketones with (thio)amides or thioureas using trifluoromethanesulfonic acid (TfOH) as a catalyst. This protocol is characterized by mild reaction conditions, metal-free, and simplicity and also features good functional group tolerance, good to excellent yields, and a broad substrate scope with more than 40 examples. Experimental studies suggest a mechanism involving 2-oxo-2-phenylethyl trifluoromethanesulfonate as the key intermediate.

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Section: Introductionmentioning

confidence: 99%

Synthesis of 2,4-Disubstituted Oxazoles and Thiazoles via Brønsted Acid-Catalyzed Cyclization of α-diazoketones with Amides

Luo,

Li,

Chen

et al. 2024

J. Org. Chem.

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TfOH‐Catalyzed Regioselective Alkylation of Hydroxybenzotriazole with Diazo Compounds and Further Base‐Facilitated Elimination under Batch and Flow Conditions

Luo,

Wang,

et al. 2024

Asian J Org Chem

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An efficient and fascinating strategy has been devised for the construction of N‐hydroxybenzotriazole (HOBt) derivatives and α‐ketoesters via TfOH‐catalyzed regioselective alkylation of N‐hydroxybenzotriazole (HOBt) and one‐pot dehydrogenation oxidation of alkylation products process under batch and flow conditions. It thus provides an expedient approach to access a range of HOBt derivatives and α‐ketoesters in good yields with high regioselectivity under mild conditions. Using flow process, less reacting time, being more environmental friendly, and process continuity ensuring higher operation safety are achieved, highlighting the practicality of the developed system.

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Access to Syn α‐Amino‐β‐Hydroxyesters by N−H Insertion on O‐Protected α‐Diazo‐β‐Hydroxyesters

Defuentes,

Lhoste,

Gaulon‐Nourry

et al. 2024

Asian J Org Chem

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The N‐H insertion reaction is a versatile method for creating C‐N bonds under mild conditions, providing in particular an efficient access to both natural and non‐natural α‐amino acid derivatives. In this field, the direct N‐H insertion on α‐diazo‐β‐hydroxyesters has not yet been investigated and constitutes a significant challenge, due to competitive migration processes. We report herein the first N‐H insertions on O‐protected α‐diazo‐β‐aryl‐β‐hydroxyesters, enabling to synthesize a wide range of α‐amino‐β‐hydroxyesters by tuning the nature of the amine and the aryl substituent. Overall, 28 N‐H insertion products have been isolated, with moderate to good yields in most cases, and diastereoisomeric ratios up to 8:1 in favor of the syn diastereoisomer.

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TfOH-Catalyzed Regioselective S–H Insertion of Cyclic Thioamide Derivatives with Diazo Compounds at Room Temperature

Cited by 8 publications

References 64 publications

Synthesis of 2,4-Disubstituted Oxazoles and Thiazoles via Brønsted Acid-Catalyzed Cyclization of α-diazoketones with Amides

Synthesis of 2,4-Disubstituted Oxazoles and Thiazoles via Brønsted Acid-Catalyzed Cyclization of α-diazoketones with Amides

TfOH‐Catalyzed Regioselective Alkylation of Hydroxybenzotriazole with Diazo Compounds and Further Base‐Facilitated Elimination under Batch and Flow Conditions

Access to Syn α‐Amino‐β‐Hydroxyesters by N−H Insertion on O‐Protected α‐Diazo‐β‐Hydroxyesters

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