Rhodium-Catalyzed Asymmetric Allylic Dearomatization of β-Naphthols with gem-Difluorinated Cyclopropanes

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4287 - 4293

Published: Feb. 25, 2025

Language: Английский

---

Photocatalytic gem‐Difluoroolefination Reactions by a Formal C−C Coupling/Defluorination Reaction with Diazoacetates

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(4)

Published: Oct. 30, 2021

The photolysis of diazoalkanes to conduct singlet carbene transfer reactions colored has recently attracted significant interest in organic synthesis. Herein, we describe a photocatalytic approach that allows the access triplet intermediates via energy highly efficient gem-difluoroolefination with α-trifluoromethyl styrenes. use tertiary amines proved pivotal unlock this unusual reaction pathway and prevent undesired cyclopropanation pathways. amine further facilitates ultimate abstraction fluoride yield gem-difluoroolefins (43 examples, up 88 % yield), which is supported by experimental theoretical mechanistic studies. We explored synthesis method broad substrate scope, ranging from simple olefins heterocyclic towards decoration pharmaceutically relevant building blocks.

Language: Английский

---

Stereoselective gem-Difluorovinylation of gem-Difluorinated Cyclopropanes Enabled by Ni/Pd Cooperative Catalysis

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(19), P. 11960 - 11965

Published: Sept. 13, 2021

A cross-electrophile coupling between gem-difluorinated cyclopropanes and 2,2-difluorovinyl tosylate via dual Ni/Pd cooperative catalysis under mild reaction conditions is presented. Various structurally unique organofluorine compounds bearing both monofluoroalkene gem-difluoroalkene moieties can be effectively afforded in good yields with a high (Z)-selectivity. The synthetic utility of this protocol has been successfully demonstrated by the late-stage modification series complex bioactive molecules.

Language: Английский

---

Nickel‐Catalyzed Defluorinative Asymmetric Cyclization of Fluoroalkyl‐Substituted 1,6‐Enynes for the Synthesis of Seletracetam

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 23, 2022

Abstract The introduction of fluorine‐containing groups into organic molecules can significantly affect their physical and chemical properties has long been used as an effective strategy for drug discovery development. Consequently, the development catalytic asymmetric methods synthesis heterocycles is highly desirable sought after. Herein, we describe a nickel‐catalyzed defluorinative cyclization fluoroalkyl‐substituted 1,6‐enynes, providing expedient access to synthetically attractive 4‐fluorovinyl‐substituted 2‐pyrrolidones in good yields with remarkable high levels chemo‐, regio‐, enantioselectivities (90–99 % ee,>35 examples). This protocol features readily available starting materials excellent functional group compatibility, exhibits complementary regioselectivity. utility this was demonstrated enantioselective antiepileptic Seletracetam.

Language: Английский

---

Pd/IPr^BIDEA-Catalyzed Hydrodefluorination of gem-Difluorocyclopropanes: Regioselective Synthesis of Terminal Fluoroalkenes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 24 - 32

Published: Oct. 13, 2023

Developing new strategies to enable chemo- and regioselective reductions is an important topic in chemical research. Herein, efficient Pd/IPr

Language: Английский

---

Synthesis of Fluorinated Compounds by Nickel-Catalyzed Defluorinative Cross-Coupling Reactions

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(18), P. 12238 - 12268

Published: Sept. 1, 2023

Organofluorine compounds have attracted extensive attention in various industrial fields due to their unique chemical and physical properties. Despite increasing demand a wide range of scientific fields, the synthesis organofluorine still faces several problems, such as difficulties handling fluorinating reagents control chemoselectivity. Compared with formation C–F bonds, activation functionalization carbon–fluorine bonds is very important but challenging topic synthetic chemistry. Due properties nickel, Ni-catalyzed defluorinative cross-couplings been greatly developed past few decades powerful strategies for construction fluorinated organic compounds. This Review summarizes advances cross-coupling aryl fluorides, gem-difluorovinyl trifluoromethyl

Language: Английский

---

Diastereoselective Synthesis of Monofluorocyclohexenes through Photocatalyzed Cascade Cyclization of gem‐Difluoroalkenes and α,β‐Unsaturated Carbonyl Compounds

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 16, 2023

Monofluoroalkenes are nonhydrolyzable mimetics of amides. Previous work focused on the synthesis non-cyclic monofluoroalkenes. However, diastereoselective monofluorocyclohexenes from substrates is challenging. Herein, we report first photocatalyzed cascade cyclization reactions readily available α,β-unsaturated carbonyl compounds and gem-difluoroalkenes for highly functionalized monofluorocyclohexenes. The reaction shows broad substrate scope with high diastereoselectivity (>30 examples, up to 86 % yield, >20 : 1 dr). post-reaction transformations products demonstrate synthetic potential this methodology.

Language: Английский

---

Copper-Mediated Radical Fluorine-Atom Transfer to Sulfonyl Radical: A Dramatic 4-Methoxypyridine 1-Oxide Ligand Effect

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3115 - 3127

Published: Feb. 13, 2024

Although the transition metal-catalyzed radical fluorine atom transfer (FAT) strategy has emerged as a powerful tool for construction of C–F bonds, to our knowledge, this approach rarely been applied formation S–F bonds. Here, we report that 4-methoxypyridine 1-oxide can serve an inexpensive and simple yet effective ligand thus promote transformation copper-mediated challengeable FAT sulfonyl radicals, paving way assembly FSO2 group. Based on concept, three Cu(I)-catalyzed protocols involving site-selective intra- intermolecular fluorosulfonylation inert C(sp3)–H bonds 1,2-aminofluorosulfonylation inactivated alkenes have developed, enabling preparation C(sp3)-rich aliphatic fluorides cannot be easily synthesized by known methods. These practical operationally methods result in high functional group tolerance under mild conditions modification bioactive derivatives highly valued molecules. Detailed mechanistic studies indicate unique role facilitating such rare FATs via outer-sphere pathway.

Language: Английский

---

Rhodium‐Catalyzed Enantio‐ and Regioselective Allylation of Indoles with gem‐Difluorinated Cyclopropanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 22, 2024

Abstract The use of gem ‐difluorinated cyclopropanes ( ‐DFCPs) as fluoroallyl surrogates under transition‐metal catalysis has drawn considerable attention recently but such reactions are restricted to producing achiral or racemic mono‐fluoroalkenes. Herein, we report the first enantioselective allylation indoles rhodium with ‐DFCPs. This reaction shows exceptional branched regioselectivity towards ‐DFCPs, which provides an efficient route enantioenriched fluoroallylated wide substrate scope and good functional group tolerance.

Language: Английский

---

Carbene‐Catalyzed Enantioselective Hydrophosphination of α‐Bromoenals to Prepare Phosphine‐Containing Chiral Molecules

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(51), P. 26616 - 26621

Published: Oct. 2, 2021

Disclosed herein is the first carbene-organocatalyzed asymmetric addition of phosphine nucleophiles to in situ generated α,β-unsaturated acyl azolium intermediates. Our reaction enantioselectively constructs carbon-phosphine bonds and prepares chiral phosphines with high optical purities. The products are suitable for transforming ligands or catalysts applications catalysis. diarylalkyl trialkyl from our catalytic reactions, air-sensitive reactive nature, can be trapped (and stored) their sulfur-oxidized form operational simplicities.

Language: Английский

---