Divergent Synthesis of Sulfur‐Containing Bridged Cyclobutanes by Lewis Acid Catalyzed Formal Cycloadditions of Pyridinium 1,4‐Zwitterionic Thiolates and Bicyclobutanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: May 31, 2024

Bridged cyclobutanes and sulfur heterocycles are currently under intense investigation as building blocks for pharmaceutical drug design. Two formal cycloaddition modes involving bicyclobutanes (BCBs) pyridinium 1,4-zwitterionic thiolate derivatives were described to rapidly expand the chemical space of sulfur-containing bridged cyclobutanes. By using Ni(ClO

Language: Английский

---

Indolizine Synthesis through Annulation of Pyridinium 1,4‐Thiolates and Copper Carbenes: A Predictive Catalysis Approach

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(5), P. 760 - 766

Published: Feb. 8, 2023

Abstract Predictive catalysis was applied to the reaction of pyridinium 1,4‐zwitterionic thiolates with a copper carbene. Theoretical calculations were first performed determine suitability their annulation and make predictions about performance different salts, diazo species, derivatives. With in hand, experimental conditions optimized, scope assessed, precision evaluated. Yields up 90% obtained for synthesis indolizine scaffolds reactivity metal magnified image

Language: Английский

---

Chameleonic Reactivity of Imidoyl Sulfoxonium Ylides: Access to Functionalized Pyrroles and Dihydro-pyridines

Organic Letters, Journal Year: 2024, Volume and Issue: 26(1), P. 62 - 67

Published: Jan. 3, 2024

We have found a chameleonic reactivity of imidoyl sulfoxonium ylides. On the one hand, ylides react with electron-deficient reagents, such as alkynyl esters, to lead formation 1,2-dihydro-pyridines. The methyl group attached sulfur atom acts methylene donor. other pyridinium 1,4-zwitterionic thiolates, which leads functionalized pyrroles. Both transformations feature mild reaction conditions and good functional tolerance.

Language: Английский

---

Recent advances in the cyclization reactions of pyridinium 1,n-zwitterions (n = 4 and 5): scope and mechanism

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(11), P. 2813 - 2829

Published: Jan. 1, 2023

This review summarizes the recent advances in cyclization reactions involving pyridinium 1, n -zwitterions ( = 4 and 5) highlights applications of efficient construction heterocycles.

Language: Английский

---

Highly Stereoselective [2 + 4] Annulation of Phosphenes and Enones with β-Electron-Donating Groups

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

Published: March 22, 2025

Enones with β-electron-donating groups can exist in their zwitterionic resonance forms, which favor nucleophilic attack to phosphenes generated from phosphoryl (aryl)diazomethanes under blue light irradiation yield intermediates. The intermediates cyclize afford highly stereoselective trans-3,4-dihydro-1,2-oxaphosphinine 2-oxides good excellent yields. In the cyclic transition state of final cyclization, stereoelectronic effect and Coulomb force control high stereoselectivity. electron-donating enones play double roles both cyclization. reaction features readily available starting materials, atom-economy, no catalyst, a fast rate, broad functional group-tolerance substrate scope, yields stereoselectivity, mild conditions.

Language: Английский

---

Divergent Synthesis of Sulfur‐Containing Bridged Cyclobutanes by Lewis Acid Catalyzed Formal Cycloadditions of Pyridinium 1,4‐Zwitterionic Thiolates and Bicyclobutanes

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(40)

Published: May 31, 2024

Abstract Bridged cyclobutanes and sulfur heterocycles are currently under intense investigation as building blocks for pharmaceutical drug design. Two formal cycloaddition modes involving bicyclobutanes (BCBs) pyridinium 1,4‐zwitterionic thiolate derivatives were described to rapidly expand the chemical space of sulfur‐containing bridged cyclobutanes. By using Ni(ClO 4 ) 2 catalyst, an uncommon higher‐order (5+3) BCBs with quinolinium was achieved broad substrate scope mild reaction conditions. Furthermore, first Lewis acid‐catalyzed asymmetric polar BCB pyridazinium accomplished. In contrast, thiolates undergo Sc(OTf) 3 ‐catalyzed (3+3) generate thia‐norpinene products, which represent initial instance synthesizing 2‐thiabicyclo[3.1.1]heptanes (thia‐BCHeps) from BCBs. Moreover, we have successfully used this protocol prepare thia‐BCHeps‐substituted analogues bioactive molecule Pitofenone. Density functional theory (DFT) computations imply that kinetic factors govern between thiolate, whereas is thermodynamic control.

Language: Английский

---

Transition-Metal-Free Radical Approach for the Synthesis of Isothiocyanates by Pyridinium 1,4-Zwitterionic Thiolates as a Sulfur Source

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Herein, we disclose a novel, mild, transition-metal-free approach to synthesizing diversely functionalized isothiocyanates from the corresponding isocyanide precursors, achieving high excellent yields (up 97%). The current method sheds light on reactivity of pyridinium 1,4-zwitterionic thiolates as an unprecedented sulfur source strikingly distinct their previously known in ionic annulation reactions, showcasing innovative organic synthesis.

Language: Английский

---

Copper(I) Iodide Catalyzed [3 + 3] Annulation of Iodonium Ylides with Pyridinium 1,4-Zwitterionic Thiolates for the Synthesis of 1,4-Oxathiin Scaffolds

Organic Letters, Journal Year: 2023, Volume and Issue: 25(26), P. 4830 - 4834

Published: June 26, 2023

The selective assembly of the 1,4-oxathiin nucleus has been treated as a powerful strategy to access this scaffold present in molecules with very interesting properties. In study, chameleon-like reactivity pyridinium 1,4-zwitterionic thiolates is exploited assemble core through [3 + 3] annulation. optimal annulation partner found be iodonium ylide cyclic 1,3-diketones. developed protocol allows synthesis variety bicyclic derivatives under mild conditions copper(I) iodide catalysis. Access benzoannulated 1,4-oxathiins achieved iodine-mediated aromatization initially obtained compounds.

Language: Английский

---

Photoredox Catalyzed [3 + 2]-Annulation Reaction of Pyridinium 1,4-Zwitterionic Thiolates with Alkenes: Synthesis of Dihydrothiophenes

Organic Letters, Journal Year: 2023, Volume and Issue: 25(33), P. 6105 - 6109

Published: Aug. 16, 2023

Pyridinium 1,4-zwitterionic thiolates are usually used to develop ionic annulation reactions. However, radical reactions were rare. We developed a photoredox catalyzed [3 + 2]-annulation reaction of pyridinium with alkenes, disclosed the new reactivity thiolate, and provided synthetic method for dihydrothiophene.

Language: Английский

---

Divergent access to fused N-heterocycle-thiazolines by solvent-dependent reaction of isoquinolinium thiolates with silylketene acetals

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(40), P. 6032 - 6035

Published: Jan. 1, 2023

A solvent-dependent strategy for the selective synthesis of isoquinuclidine- and tetrahydroisoquinoline thiazoline N , S -heterocycles from isoquinolinium 1,4-zwitterionic thiolates silylketene acetals is reported.

Language: Английский

---