Interrupted CuAAC‐Thiolation for the Construction of 1,2,3‐Triazole‐Fused Eight‐Membered Heterocycles from <i>O</i>‐/<i>N</i>‐Propargyl derived Benzyl Thiosulfonates with Organic Azides

Reddy, Raju Jannapu; Waheed,; Arram, Haritha Kumari; Krishna, G. Rama

doi:10.1002/adsc.202101256

Cited by 20 publications

(6 citation statements)

References 67 publications

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“…Based on the mechanistic studies and literature precedents, , a plausible mechanism for the copper-mediated intramolecular interrupted CuAAC selanylation is proposed in Scheme . First, the desilylation reaction of the TMS–acetylene ( 4a ) occurs in the presence of CuF 2 (method B).…”

Section: Resultsmentioning

confidence: 99%

“…It is important to highlight that the formation of 5- H -1,2,3-triazole (8) and ( 9) (see Scheme ) was not observed under the standard reaction conditions, even when water or acetic acid was positively added to the reaction media (Scheme e). These results contrast with earlier literature reports, where a significant amount of byproduct 5- H -1,2,3-triazole resulting from concomitant proto-demetallation of the cuprate-triazole is observed. , …”

Section: Resultsmentioning

confidence: 99%

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Copper-Mediated Intramolecular Interrupted CuAAC Selanylation

et al. 2023

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We, herein, describe a copper-mediated domino CuAAC intramolecular selanylation for the synthesis of unprecedented fused benzo[4,5][1,3]selenazolo[3,2-c][1,2,3]triazoles from 1,2-bis(2-azidoaryl)diselenides and terminal alkynes under microwave irradiation. This is the seminal method for the synthesis of these fused heterocycles, and it proceeds under mild conditions, tolerates several functional groups, and can be carried out using environmentally benign solvents such as dimethyl carbonate. This transformation has been successfully extended to TMS-protected alkynes and to bioactive alkynes. A plausible reaction mechanism is proposed based on several control experiments and previous reports.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Copper-Mediated Intramolecular Interrupted CuAAC Selanylation

et al. 2023

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“…In this way, the azide component can be avoided. [51] The proposed mechanism of action starts with the formation of the metallocycle 78, which undergoes oxidative addition with the thiosulfonate to form a Cu (III) complex 79, which then rapidly undergoes reductive elimination to yield the final product 77. It is worth noting that in this reaction, the optimal solvent appears to be a protic solvent such as EtOH, which is generally avoided in other interrupted click reactions discussed earlier (Scheme 29).…”

Section: Intramolecular Interrupted Click Reactionsmentioning

confidence: 99%

Each Interruption is an Opportunity: Novel Synthetic Strategies Explored Through Interrupted Click Reactions

Brunelli,

Russo,

Giustiniano

et al. 2024

Chemistry A European J

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The particular and unique mechanism of the copper‐catalyzed reaction between azides and alkynes (CuAAC) has not only allowed for the efficient synthesis of 1,2,3‐trisubstituted 1,4‐triazoles in excellent yields and under mild conditions, becoming the quintessential click reaction, but it has also enabled the straightforward formation of a metallocycle intermediate, the copper triazolyl. This, under suitable reaction conditions able to suppress its protonolysis, can be used either for the creation of new bicyclic triazolyl structures or for the generation of novel three or four‐component reactions. The aim of this review is to rationalize and unify all these transformations, which are collectively referred to as “interrupted click reactions”.

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“…Following our continuous efforts in organosulfur chemistry and the exploration of ( E )-β-iodovinyl sulfones, we assumed that multifunctional β-iodovinyl sulfones could be expedient precursors for the installation of a vinyl sulfone moiety on the benzofuran scaffold. Very recently, we reported a base-mediated oxa-Michael addition–elimination of ( E )-β-iodovinyl sulfones with o -alkynylphenols, followed by cycloisomerization and unique sulfonyl migration under the influence of Mn(OAc) 3 ·2H 2 O to provide vinyl sulfone-tethered chromenes in moderate to high yields (Scheme c) .…”

Section: Introductionmentioning

confidence: 99%

Pd(II)-Catalyzed Tandem Cycloannulative-Alkenylation of o-Alkynyl-Phenols/Anilines with (E)-β-Iodovinyl Sulfones: A Direct Strategy To Construct 3-(Vinyl sulfonyl)benzoheterole Derivatives

2023

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Benzoheteroles and vinyl sulfones are the most promising pharmaceutical relevance motifs, yet the hybrid analogues of these scaffolds still need to be explored. We report herein a general and highly efficient Pd(OAc)2-catalyzed intramolecular cyclization and vinylation of o-alkynylphenols/o-alkynylanilines with (E)-β-iodovinyl sulfones under mild reaction conditions. A direct C(sp2)–C(sp2) cross-coupling is enabled for the diversity-oriented synthesis of vinyl sulfone-tethered benzofurans and indoles in good to high yields with excellent stereoselectivity. Notably, this tandem process was consistent at the gram scale, and in situ, generation of 2-(phenylethynyl)phenol has also been utilized in a scalable synthesis. Late-stage synthetic transformations were also further explored, including isomerization and desulfonylative-sulfenylation. Moreover, several control experiments were accomplished, and we proposed a plausible mechanism based on existing experimental results.

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Interrupted CuAAC‐Thiolation for the Construction of 1,2,3‐Triazole‐Fused Eight‐Membered Heterocycles from O‐/N‐Propargyl derived Benzyl Thiosulfonates with Organic Azides

Cited by 20 publications

References 67 publications

Copper-Mediated Intramolecular Interrupted CuAAC Selanylation

Copper-Mediated Intramolecular Interrupted CuAAC Selanylation

Each Interruption is an Opportunity: Novel Synthetic Strategies Explored Through Interrupted Click Reactions

Pd(II)-Catalyzed Tandem Cycloannulative-Alkenylation of o-Alkynyl-Phenols/Anilines with (E)-β-Iodovinyl Sulfones: A Direct Strategy To Construct 3-(Vinyl sulfonyl)benzoheterole Derivatives

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