Highly Diastereoselective Synthesis of 5/6-Fused Bicyclic Ring Systems via Radical Cyano Group Migration

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

Published: March 3, 2025

Here we report a highly diastereoselective cyano group transfer radical cyclization reaction to construct 5/6-fused bicyclic ring systems that bear three contiguous and congested stereogenic elements, with 100% atom economy under catalyst-free near-ultraviolet light irradiation conditions. Mechanistic investigations density functional theory calculations suggest the diastereoselectivity is governed by conformational distribution of triplet diradical intermediate rate reverse intersystem crossing (RISC) before coupling.

Language: Английский

---

Dialkylation of Alkenes to Fluorinated δ-Lactams Enabled by Nickel-Electron-Shuttle Catalysis

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

Published: March 24, 2025

The δ-lactam motif is a privileged pharmacophore in drug design and development. While these biologically relevant molecules could be assembled through two-component cyclization, modular approach to constructing structures via multicomponent reaction with unactivated alkenes as starting materials rare. Herein, we report tandem that integrates alkene-dialkylation radical-involved ring-opening cyclization under single metal-electron-shuttle catalysis, which represents the most expeditious access fluorinated δ-lactams from simple alkenes.

Language: Английский

---

Iron-Catalyzed Alkylative Aminosulfonylation of Alkenes and Alkynes via Radical-Anion Relay

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

Published: May 19, 2025

A novel Fe-catalyzed alkylative aminosulfonylation of alkenes and alkynes with alkyl halides O-Ts activated hydroxylamines by using Na2S2O4 as a reductant sulfone source has been developed. The metal-electron-shuttle catalysis was discovered to be vital for the highly efficient generation sulfonyl radicals anions without requiring organometallic intermediates. This method provides access sulfonamides from easily available features broad substrate scope.

Language: Английский

---

Overcoming Electron Bias in Hydroarylation of Phenylpropiolic Acid Derivatives To Enable Highly Reversed Regio- and Stereoselectivity via Steric and Transient Post Addition Coordination

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(13), P. 9985 - 9992

Published: June 19, 2024

The regio- and stereoselective hydroarylation of internal alkynes via transition-metal catalysis offers a direct approach for designing highly stereodefined multifunctionalized olefins. Through recognition electronic bias, β-syn-hydroarylation poor with arylboronic acids has been well studied. However, from the same starting materials, achieving opposite α-selective anti-stereoselective remains significant challenge due to these inherent biases. Therefore, an alternative synthetic pathway trisubstituted alkenes reversed positioning configuration substituents is desirable. Based on steric repulsion-induced regioselectivity transient post-addition coordination-directed stereoselectivity, we report herein α-hydroarylation method phenylpropiolic esters using nickel catalyst that promotes formal anti-addition pathway. A broad range organoboronic acid derivatives are compatible this protocol, offering selectivity traditional reactions. distinct advantages our include precise control over selectivity, reduced loading, tolerance toward functional groups. These features highlight potential in synthesis late-stage modification alkyne-based drug intermediates, showcasing its versatility applicability organic synthesis.

Language: Английский

---

Metal electron-shuttle catalysis

Trends in Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 1, 2024

Language: Английский

---