Mendeleev Communications, Journal Year: 2024, Volume and Issue: 34(5), P. 698 - 700
Published: Sept. 1, 2024
Language: Английский
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
Citations
15
Chemical Communications, Journal Year: 2024, Volume and Issue: 60(28), P. 3764 - 3773
Published: Jan. 1, 2024
This feature article summarizes our efforts towards developing Rh-catalyzed reactions of gem -difluorinated cyclopropanes, briefly discussing the design, selectivity, mechanisms and future research prospects.
Language: Английский
Citations
12
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: May 21, 2024
Abstract Transition-metal catalyzed allylic substitution reactions of alkenes are among the most efficient methods for synthesizing diene compounds, driven by inherent preference an inner-sphere mechanism. Here, we present a demonstration outer-sphere mechanism in Rh-catalyzed reaction simple using gem -difluorinated cyclopropanes as allyl surrogates. This unconventional offers opportunity fluorine recycling via C − F bond cleavage/reformation, ultimately delivering carbofluorination products. The developed method tolerates wide range alkenes, providing access to secondary, tertiary fluorides and -difluorides with 100% atom economy. DFT calculations reveal that formation goes through unusual nucleophilic allyl-Rh species instead migration insertion, generated carbon cation then forms tetrafluoroborate fluoride shuttle.
Language: Английский
Citations
9
Advanced Science, Journal Year: 2024, Volume and Issue: 11(18)
Published: March 9, 2024
Abstract Transition‐metal (TM) catalyzed reaction of gem ‐difluorinated cyclopropanes ( ‐DFCPs) has drawn much attention recently. The generally occurs via the activation distal C─C bond in ‐DFCPs by a low‐valent TM through oxidative addition, eventually producing mono‐fluoro olefins as coupling products. However, achieving regioselective proximal that overcomes intrinsic reactivity catalysis remains elusive. Here, new mode enabled high‐valent copper catalysis, which allows exclusive congested is presented. achieves fluoroarylation uses NFSI (N‐fluorobenzenesulfonimide) electrophilic fluoro reagent and arenes C─H nucleophiles, enabling synthesis diverse CF 3 ‐containing scaffolds. It proposed species plays an important role possibly σ‐bond metathesis.
Language: Английский
Citations
6
Chemical Science, Journal Year: 2024, Volume and Issue: 15(34), P. 13800 - 13806
Published: Jan. 1, 2024
Metathesis reactions have been established as a powerful tool in organic synthesis. While great advances were achieved double-bond metathesis, like olefin metathesis and carbonyl single-bond has received less attention the past decade. Herein, we describe first C(sp
Language: Английский
Citations
5
The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown
Published: April 18, 2025
We report an efficient palladium-catalyzed ring-opening defluorinative Hiyama cross-coupling of gem-difluorocyclopropanes with structurally diverse (hetero)arylsilanes through C-C bond activation and C-F cleavage. This regioselective features a broad substrate scope excellent functional group compatibility, affording variety linear 2-fluoroallylic scaffolds in good yields high Z-selectivity.
Language: Английский
Citations
0
Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(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
Citations
1
Mendeleev Communications, Journal Year: 2024, Volume and Issue: 34(5), P. 698 - 700
Published: Sept. 1, 2024
Language: Английский
Citations
0