Organoelectrocatalytic cyclopropanation of alkenyl trifluoroborates with methylene compounds DOI Creative Commons
Yi Wei, Xu Pengcheng, Tianyu He

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 7, 2024

Cyclopropanes are not only privileged motifs in many natural products, agrochemicals, and pharmaceuticals, but also highly versatile intermediates synthetic chemistry. As such, great effort has been devoted to the cyclopropane construction. However, novel catalytic methods for cyclopropanation with two abundant substrates, mild conditions, high functional group tolerance, broad scope still desirable. Herein, we report an intermolecular electrocatalytic of alkenyl trifluoroborates methylene compounds. The reaction uses simple diphenyl sulfide as electrocatalyst under base-free conditions. And thus, a various compounds well vinyltrifluoroborates is demonstrated, including styrenyl, 1,3-dienyl, fluorosulfonyl, base-sensitive substrates. Preliminary mechanistic studies presented, revealing critical role boryl substituent facilitate desired pathway water hydrogen atom source.

Language: Английский

Advances in the Synthesis of Cyclopropylamines DOI
Philippe Bertus,

Julien Caillé

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

Cyclopropylamines are an important subclass of substituted cyclopropanes that combine the unique electronic and steric properties with presence a donor nitrogen atom. In addition to their in diverse array biologically active compounds, cyclopropylamines utilized as synthetic intermediates, particularly ring-opening or cycloaddition reactions. Consequently, synthesis these compounds has constituted significant research topic, evidenced by abundant published methods. widely used Curtius rearrangement, classical cyclopropanation methods have been adapted integrate function (Simmons-Smith reaction, metal-catalyzed reaction diazo on olefins, Michael-initiated ring-closure reactions) advances enantioselective synthesis. More recently, specific developed for preparation aminocyclopropane moiety (Kulinkovich reactions applied amides nitriles, cyclopropenes, involving C-H functionalization, ...). The topic this review is present different cyclopropylamine derivatives, aim covering methodological best possible, highlighting scope, stereochemical aspects future trends.

Language: Английский

Citations

1
Flow Electroreductive Nickel‐Catalyzed Cyclopropanation of Alkenes Using gem‐Dichloroalkanes DOI Creative Commons
Morgan Regnier, Clara Vega, Dimitris I. Ioannou

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

Abstract Cyclopropanes are valuable motifs in organic synthesis, widely featured pharmaceuticals and functional materials. Herein, we report an efficient electrochemical methodology for the cyclopropanation of alkenes, leveraging a nickel‐catalyzed process continuous‐flow. The developed protocol demonstrates broad substrate scope, accommodating both electron‐rich electron‐poor alkenes with high group tolerance. Beyond dichloromethane as feedstock methylene source, enables synthesis methylated, deuterated, chloro‐substituted cyclopropanes. Mechanistic investigations suggest electro‐generation nickel carbene key intermediate. Notably, reaction operates under ambient conditions, tolerates air moisture, achieves scalability through continuous‐flow technology, offering straightforward route to multi‐gram quantities enhanced throughput.

Language: Английский

Citations

0
Building Efficient Diastereo- and Enantioselective Synthetic Routes to trans-Cyclopropyl Esters for Rapid Lead Scale-Up DOI Creative Commons
Christophe Allais,

Louise Bernier,

David C. Blakemore

et al.

Organic Process Research & Development, Journal Year: 2025, Volume and Issue: unknown

Published: March 3, 2025

Language: Английский

Citations

0
Synthesis of α-Substituted Cyclic Boronates via Titanium-Catalyzed Cyclization of Vinyl Boronates with Dihaloalkanes DOI Creative Commons

Ximei Tian,

Lipeng Wu

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A titanium-catalyzed reductive cyclization of vinyl boronates with gem -dihaloalkanes is developed. α-Substituted cyclic that are otherwise difficult to access, such as those heteroatom-containing rings, readily obtained.

Language: Английский

Citations

0
Synthesis of constrained bicycloalkanes through bibase-promoted brook rearrangement/radical-polar crossover cyclization DOI Creative Commons

Xinke Ouyang,

Bingyao Shi,

Yuanyuan Zhao

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(28), P. 11092 - 11098

Published: Jan. 1, 2024

A concise protocol for the synthesis of constrained bicycloalkanes has been developed, using easily obtainable α-silyl alcohols and alkenes through a bibase-promoted brook rearrangement/radical-polar crossover cyclization (RPCC) process.

Language: Английский

Citations

3
Visible‐Light Photocatalytic Cyclopropanation of Alkenes with Dibromomethane DOI

Yiqiang Tian,

Yuekun Zhang,

Jiapan Niu

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(21)

Published: July 9, 2024

Abstract The cyclopropane unit plays a crucial role in pharmaceutical compound design and organic transformation. In this study, we have developed novel redox‐neutral photocatalytic cyclopropanation method involving dibromomethane alkenes. This chemistry enables the synthesis of valuable functional group‐substituted cyclopropanes using readily available starting materials practical reaction conditions. Additionally, demonstrated versatility products as precursors for various derivatives with different substituents. Importantly, protocol facilitates key found specific type T‐type calcium channel blocker. Furthermore, proposed mechanism is well‐supported by control experiments.

Language: Английский

Citations

2
Organoelectrocatalytic cyclopropanation of alkenyl trifluoroborates with methylene compounds DOI Creative Commons
Yi Wei, Xu Pengcheng, Tianyu He

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 7, 2024

Cyclopropanes are not only privileged motifs in many natural products, agrochemicals, and pharmaceuticals, but also highly versatile intermediates synthetic chemistry. As such, great effort has been devoted to the cyclopropane construction. However, novel catalytic methods for cyclopropanation with two abundant substrates, mild conditions, high functional group tolerance, broad scope still desirable. Herein, we report an intermolecular electrocatalytic of alkenyl trifluoroborates methylene compounds. The reaction uses simple diphenyl sulfide as electrocatalyst under base-free conditions. And thus, a various compounds well vinyltrifluoroborates is demonstrated, including styrenyl, 1,3-dienyl, fluorosulfonyl, base-sensitive substrates. Preliminary mechanistic studies presented, revealing critical role boryl substituent facilitate desired pathway water hydrogen atom source.

Language: Английский

Citations

2