Advances in organocatalytic asymmetric [3 + 3] cycloadditions: synthesis of chiral six-membered (hetero)cyclic compounds

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(19), P. 5573 - 5604

Published: Jan. 1, 2024

This review has summarized the development of organocatalytic asymmetric [3 + 3] cycloadditions and given insights into remaining challenges to promote future this field.

Language: Английский

---

Asymmetric aza‐Friedel–Crafts Reaction of Cyclic Ketimines with 5‐Aminopyrazole Derivatives: Expedient Access to Pyrazole‐Based C2‐quaternary Indolin‐3‐Ones

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(20)

Published: Jan. 5, 2023

A chiral phosphoric acid-catalyzed enantioselective aza-Friedel-Crafts reaction of 5-aminopyrazole derivatives with cyclic ketimines attached to a neutral functional group is reported. This protocol allows the formation pyrazole-based C2-quaternary indolin-3-ones high enantioselectivities and regioselectivities. Moreover, gram-scale synthesis 5-aminopyrazole-based was performed, no decrease in yield enantioselectivity.

Language: Английский

---

Chiral organophosphates as ligands in asymmetric metal catalysis

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 3080 - 3109

Published: Jan. 1, 2023

Chiral phosphates have successfully been used as ligands in asymmetric metal-catalysis. This Minireview discusses the most recent examples, including main-group catalysis, transition-metal catalysis and by rare-earth metals.

Language: Английский

---

Bipyridine-N,N′-dioxides Catalysts: Design, Synthesis, and Application in Asymmetric Synthesis of 1H-Pyrazolo[3,4-b]pyridine Analogues

Organic Letters, Journal Year: 2024, Volume and Issue: 26(17), P. 3487 - 3492

Published: April 18, 2024

A novel type of highly efficient chiral C2-symmetric bipyridine-N,N′-dioxides ligand application in catalyzing Michael addition/Cyclization 5-aminopyrazoles with α,β-unsaturated 2-acyl imidazoles has been developed, affording the corresponding adducts 85–97% yield up to 99% enantioselectivity under mild conditions a lower catalyst loading and broad scope. Remarkably, this protocol exhibits advantages terms reactivity enantioselectivity, giving fact that as low 2.2 mol % L1 2.0 Ni(OTf)2 can promote title reaction on gram scale afford desired product excellent enantioselectivity.

Language: Английский

---

Enantioselective construction of chiral gem-difluorinated C2-quaternary indoline via dual MgSO₄–CPA-catalyzed asymmetric Mannich reactions

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(5), P. 1430 - 1436

Published: Jan. 1, 2024

Herein, the synthesis of 2-(3,3-difluoro-2-phenylindolin-2-yl)-1-phenylethan-1-one scaffolds through asymmetric Mannich reactions between 3,3-difluoro cyclic ketimines and simple ketones is described.

Language: Английский

---

Asymmetric synthesis of 1H-pyrazolo[3,4-b]pyridine analogues catalyzed by chiral-at-metal Rh(iii) complexes

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(19), P. 5385 - 5389

Published: Jan. 1, 2024

An efficient asymmetric Friedel–Crafts-type alkylation/cyclization of 5-aminopyrazoles has been developed, affording corresponding pyrazolo[3,4- b ]pyridine analogues.

Language: Английский

---

Chiral Phosphoric Acid-Catalyzed Asymmetric Synthesis of Axially Chiral Arylpyrazole

Organic Letters, Journal Year: 2025, Volume and Issue: 27(4), P. 932 - 936

Published: Jan. 23, 2025

A chiral phosphoric acid-catalyzed efficient, operationally simple, general method for straightforward syntheses of axially arylpyrazole employing N-alkyl 3-aryl-5-aminopyrazoles reacting with azonaphthalenes was achieved. wide variety heterobiaryl diamines in generally good yields excellent enantioselectivities were obtained under mild conditions. In addition, a scaled-up experiment and postmodification the product further highlighted synthetic utility.

Language: Английский

---

Vinylogous functionalization of 4-alkylidene-5-aminopyrazoles with methyl trifluoropyruvates

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 533 - 540

Published: March 10, 2025

A valuable vinylogous addition reaction between 4-alkylidene-5-aminopyrazoles and alkyl trifluoropyruvates leading to highly functionalized tertiary alcohols bearing a trifluoromethyl group pyrazole ring is presented. The corresponding are obtained in moderate good yields (up 80%) high diastereoselectivity 7:1).

Language: Английский

---

Recent Advancement in H₈–BINOL Catalyzed Asymmetric Methodologies

ACS Omega, Journal Year: 2023, Volume and Issue: 8(20), P. 17381 - 17406

Published: May 11, 2023

H8–BINOL, a partially reduced form of BINOL, is widely employed in broad array organocatalyzed asymmetric methodologies. Over the last 25 years, organocatalysis has witnessed an incredible improvement, and advancement still continues to get single enantio-enriched product. The broad-spectrum applications H8–BINOL organocatalyst C–C bond formation, C-heteroatom construction, name reactions, pericyclic one pot multicomponent reaction are attracting attention researchers. A diversified unique H8–BINOL-based catalyst been synthesized screened for catalytic activity. In this Review we frame out catalyzed novel discoveries from two decades.

Language: Английский

---

Atroposelective Construction of Naphthylpyrazoles by Chiral Phosphoric Acid Catalyzed Enantioselective Cross‐Coupling of Pyrazoles with Naphthoquinone Esters

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(23)

Published: April 10, 2024

Abstract The catalytic asymmetric reaction of 5‐aminopyrazoles with naphthoquinone esters has been established. A wide range unprecedented axially chiral naphthylpyrazole derivatives (29 examples) have synthesized in moderate to excellent yields (up 99 % yield) enantioselectivities ee) by utilizing phosphoric acid as a catalyst. This protocol features mild conditions, broad substrate scope, good scalability and facile derivatization. Moreover, preliminary mechanistic investigation was conducted elucidate the mechanism.

Language: Английский

---