Divergent Synthesis of (E)- and (Z)-Alkenones via Photoredox C(sp3)–H Alkenylation–Dehydrogenation of o-Iodoarylalkanols with Alkynes DOI

Liang Zeng,

Yin Zhang,

Ming Hu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(47), P. 10096 - 10101

Published: Nov. 15, 2024

A photoredox C(sp3)–H alkenylation–dehydrogenation of o-iodoarylalkanols with terminal alkynes for the synthesis (E)- and (Z)-quaternary carbon center-containing pent-4-en-1-ones is described. The stereoselectivity depends on utilization photocatalysts. While using an organic photocatalyst like 4-DPAIPN manipulates arylalkynes to assemble (E)-pent-4-en-1-ones, in case Ir potocatalyst such as Ir(ppy)2(dtbbpy)PF6 reaction delivers (Z)-pent-4-en-1-ones. For alkylalkynes, furnishes (E)-pent-4-en-1-ones exclusively presence or Ir(ppy)2(dtbbpy)PF6.

Language: Английский

On the Existence and Relevance of Copper(III) Fluorides in Oxidative Trifluoromethylation DOI
Noel Nebra, Daniel Joven‐Sancho

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: June 24, 2024

Abstract Numerous reports invoke CuIII–F intermediates engaging in oxidative cross-couplings mediated by low/mid-valent copper and formal sources of ‘F+’ oxidants. These elusive typically instable CuIII fluorides have been rarely characterized or spectroscopically identified, making their existence participation within catalytic cycles somehow questionable. We authenticated a stable organocopper(III) fluoride that undergoes Csp–CF3 bond formation upon addition silyl-capped alkynes following 2 e– CuIII/CuI redox shuttle. This finding strongly supports the intermediacy C–C coupling. review herein state art about well-defined enabling cross-coupling reactions. 1 Introduction Brief History Coupling-Competent Fluorides 3 Design an Isolable – yet Reactive Organocopper(III) Fluoride 4 Alkyne Trifluoromethylation: Scope Mechanism 5 Extension to Aryl–CF3 C–Heteroatom Couplings 6 Summary Outlook

Language: Английский

Citations

1
One‐Pot Reactions of Ynones with Isothiocyanates for Accessing 2‐Aminothiophenone and Indole‐Fused/Indole‐Substituted Thiophenone Derivatives DOI

Zefeng Jin,

LI Cui-ying,

Guodong Shen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(24), P. 5151 - 5159

Published: Aug. 29, 2024

Abstract A copper or silver‐catalyzed cascade addition/5‐ exo‐dig cyclization/isomerization reaction of isothiocyanate with ynone has been developed. This strategy enables the synthesis a variety ( Z )‐2‐ylidene‐5‐aminothiophen‐3‐one derivatives diverse substitutions in single vessel. The method is featured pot‐economy as well regio‐ and ‐selectivity. Several biologically active molecules could be modified using this strategy. Moreover, relevant indole‐fused indole‐substituted thiophenone were also assembled one pot by merging other bond formation methods. Based on experiments related reports, pathway triggered addition ynone‐derived radical towards C( sp )‐atom was proposed to elucidate probable process transformation.

Language: Английский

Citations

0
Divergent Synthesis of (E)- and (Z)-Alkenones via Photoredox C(sp3)–H Alkenylation–Dehydrogenation of o-Iodoarylalkanols with Alkynes DOI

Liang Zeng,

Yin Zhang,

Ming Hu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(47), P. 10096 - 10101

Published: Nov. 15, 2024

A photoredox C(sp3)–H alkenylation–dehydrogenation of o-iodoarylalkanols with terminal alkynes for the synthesis (E)- and (Z)-quaternary carbon center-containing pent-4-en-1-ones is described. The stereoselectivity depends on utilization photocatalysts. While using an organic photocatalyst like 4-DPAIPN manipulates arylalkynes to assemble (E)-pent-4-en-1-ones, in case Ir potocatalyst such as Ir(ppy)2(dtbbpy)PF6 reaction delivers (Z)-pent-4-en-1-ones. For alkylalkynes, furnishes (E)-pent-4-en-1-ones exclusively presence or Ir(ppy)2(dtbbpy)PF6.

Language: Английский

Citations

0