1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(15), P. 13108 - 13205

Published: July 19, 2022

Readily accessible and shelf-stable 1,2,3-triazole its analogues such as pyridotriazole, triazoloindole, benzotriazole, thiadiazole exist in equilibrium with their ring-opened isomers, viz., diazo compounds. These isomers could be trapped by various metal catalysts (e.g., Rh, Pd, Cu, Co, Ag, etc.) to generate the corresponding carbenoids extrusion of nitrogen. As a consequence, these unique N-heterocycles facilitate access realm N-containing complex structural motifs biological importance through denitrogenative transformations transannulations, insertions, ylide formation, rearrangements trapping diverse range coupling partners alkenes, alkynes, nitriles, carbo/heterocycles, X-H/C-X bonds, etc.). Hence, suitably substituted triazole derivatives have emerged efficient surrogates compounds for generation reactive during past decades. In this comprehensive review, we aim discuss detail remarkable advancement synthesis synthetic applications.

Language: Английский

---

Rhodium-catalyzed cascade reactions of triazoles with organoselenium compounds – a combined experimental and mechanistic study

Chemical Science, Journal Year: 2021, Volume and Issue: 12(18), P. 6362 - 6369

Published: Jan. 1, 2021

Herein, we report on our studies the reaction of organoselenium compounds with triazoles under thermal conditions using simple Rh(ii) catalysts.

Language: Английский

---

Rhodium-Catalyzed Enamine Homologation of Sulfides with Triazoles as Carbene Precursor

Organic Letters, Journal Year: 2020, Volume and Issue: 22(17), P. 6816 - 6821

Published: Aug. 13, 2020

We report on Rh(II)-catalyzed enamine homologation reactions of triazoles with cyclopropylmethyl sulfides. This reaction proceeds via Dimroth rearrangement followed by rhodium-catalyzed ylide formation. ylide, however, does not undergo classic reactions. Instead, it undergoes a selective, intramolecular alkylation to yield cyclopropylmethyl-substituted enamides. The application this was evaluated different and sulfides, which underline the special reactivity sulfides (29 examples, up 83% yield).

Language: Английский

---

Synthesis of Trisubstituted Oxazoles via Aryne Induced [2,3] Sigmatropic Rearrangement–Annulation Cascade

Organic Letters, Journal Year: 2022, Volume and Issue: 24(23), P. 4145 - 4150

Published: June 6, 2022

A transition-metal-free, [2,3] sigmatropic rearrangement-annulation cascade of 2-substituted thio/amino acetonitriles with arynes allowing the synthesis 2,4,5-trisubstituted oxazoles under mild conditions has been demonstrated. The key sulfur/nitrogen ylides were generated by initial S/N arylation followed proton transfer, which was selective rearrangement involving -CN moiety and a subsequent annulation to afford desired products in reasonable yields.

Language: Английский

---

Rhodium-Catalyzed [4 + 2]-Annulation of o-Acylanilines with N-Sulfonyl-1,2,3-triazoles: Synthesis of 3-Aminoquinolines

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 9077 - 9086

Published: June 23, 2023

Efficient synthesis of 3-aminoquinolines has been demonstrated from readily accessible N-sulfonyl-1,2,3-triazoles and o-acylaniline derivatives. This transformation involves the generation C-C C-N bonds through insertion rhodium azavinyl carbenoid into a N-H bond followed by cyclization aromatization. The important features include good functional group tolerance, indoloquinoline, isolation N-H-inserted product, potential intermediate.

Language: Английский

---

Cu(I)/Chiral Bisoxazoline-Catalyzed Enantioselective Sommelet–Hauser Rearrangement of Sulfonium Ylides

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(19), P. 12343 - 12358

Published: Sept. 3, 2020

Catalytic asymmetric thia-Sommelet–Hauser rearrangement of sulfonium ylides remains a great challenge due to its multistep reaction mechanism involving metal carbene formation, proton transfer, and [2,3]-sigmatropic rearrangement. In particular, the key problem such reactions is differentiation enantiotopic lone pair electrons sulfur, which generates ylide intermediate bearing chirality on sulfur atom. With modified chiral bisoxazoline ligand, we developed Cu(I)-catalyzed with good excellent enantioselectivities. Mechanistic studies provide insights into details mechanism.

Language: Английский

---

Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines

Chemical Science, Journal Year: 2020, Volume and Issue: 12(4), P. 1479 - 1485

Published: Nov. 23, 2020

Hexahydropyrazinoindoles are prepared in a single step from N -sulfonyl triazoles and imidazolidines. Of mechanistic importance, regiodivergent reactivity can be engineered towards the exclusive formation of 8-membered ring 1,3,6-triazocines.

Language: Английский

---

Synthesis of Dihydro-3,1-benzoxazine Derivatives from 1,3-Amino Alcohols and N-Sulfonyl-1,2,3-triazole

Organic Letters, Journal Year: 2023, Volume and Issue: 25(19), P. 3375 - 3379

Published: May 8, 2023

An efficient rhodium-catalyzed synthesis of dihydro-3,1-benzoxazine derivatives has been accomplished from aniline-derived 1,3-amino alcohols and N-sulfonyl-1,2,3-triazole. The developed reaction demonstrates the new reactivity azavinyl carbenes allows access to diverse substituted dihydro-3,1-benzoxazines in good yields. Importantly, was readily extended diols could be used for selective protection amino with N-sulfonyl-1,2,3-triazole as protecting reagent.

Language: Английский

---

Cascade Reaction of α-Aryl Vinyl and Propargyl Sulfonium Salts with Carbon Nucleophiles: Synthesis of Functionalized Benzyl and Homoallyl Thioethers

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A cascade reaction of α-aryl vinyl and propargyl sulfonium salts with C-nucleophiles afforded functionalized thioethers via Michael addition followed by [2,3]-sigmatropic rearrangement.

Language: Английский

---

Carbonyl vs Hydroxy: Rhodium catalyzed carbonyl ylide triggered diastereoselective synthesis of 2,5-methano-1,3-benzoxazepines

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

A general and efficient rhodium catalyzed chemoselective reaction of N-sulfonyl-1,2,3-triazoles with 2-hydroxyphenyl substituted enone has been successfully accomplished. The occurs through the initial azavinyl carbenes to carbonyl group followed by rearrangement cyclization. tolerated various functional groups allowed synthesis 2,5-methano-1,3-benzoxazepines in high yield as single diastereomer. Control experiments revealed formation potential dihydropyrrole an intermediate aided proposing plausible mechanism.

Language: Английский

---