Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(4), P. 1057 - 1061
Published: Dec. 15, 2023
This work describes a ligand-controlled regioselective ring-opening/defluorinative annulation of gem -DFCPs with enaminones, which provides an alternative strategy for the divergent synthesis pyrroles.
Language: Английский
Science, Journal Year: 2023, Volume and Issue: 381(6665), P. 1474 - 1479
Published: Sept. 28, 2023
Nitrogen scanning in aryl fragments is a valuable aspect of the drug discovery process, but current strategies require time-intensive, parallel, bottom-up synthesis each pyridyl isomer because lack direct carbon-to-nitrogen (C-to-N) replacement reactions. We report site-directable C-to-N reaction allowing unified access to various pyridine isomers through nitrene-internalization process. In two-step, one-pot procedure, azides are first photochemically converted 3
Language: Английский
Citations
95
ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4287 - 4293
Published: Feb. 25, 2025
Language: Английский
Citations
3
ChemCatChem, Journal Year: 2022, Volume and Issue: 14(24)
Published: Aug. 11, 2022
Abstract gem ‐Difluorocyclopropanes (F 2 CPs) have aroused considerable attention not only from the structural perspective but also due to their ability participate in various valuable transformations. This Review summarizes advances catalytic ring‐opening reactions of ‐F CPs, especially emphasizing reactivities and applications those non‐activated ones under transition‐metal catalysis. Their achievements, synthetic limitations are discussed with aim stimulate enthusiasm for further development.
Language: Английский
Citations
48
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)
Published: April 4, 2023
Defluorinative manipulation of polyfluorinated molecules has shown great promise due to its granting synthetic versatility inert C-F bonds. The development chemo-, stereo- and regioselective strategies realize highly efficient formation either the linear/branched or E/Z products from gem-difluorocyclopropanes (gem-F2 CPs) is a challenging task. Herein, we have realized palladium/NHC-catalyzed fluoroallylation/annulation hydrazones with gem-F2 CPs that incorporate hydrazone N2 moiety into products. thermodynamically unstable fluorinated E-allylation aryl ketone were obtained for first time, while di-alkyl yielded monofluorinated branched selectivity under similar reaction conditions. With aldehyde hydrazones, two kinds pyrazoles via defluorinative allylation/annulation cascade, in which different carbon atoms could be incorporated pyrazole rings regiospecifically. DFT calculations revealed divergent was kinetically controlled final C-C bond proceeded through 7-membered TS.
Language: Английский
Citations
36
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
Citations
35
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)
Published: June 20, 2023
Direct synthesis of gem-difluorinated carbocyclic molecules represents a longstanding challenge in organic chemistry. Herein, Rh-catalyzed [3+2] cycloaddition reaction between readily available cyclopropanes (gem-DFCPs) and internal olefins has been developed, enabling the efficient cyclopentanes with good functional group compatibility, excellent regioselectivity diastereoselectivity. The resulting products can undergo downstream transformations to access various mono-fluorinated cyclopentenes cyclopentanes. This demonstrates use gem-DFCPs as type "CF2 " C3 synthon for under transition metal catalysis, which provides potential strategy synthesizing other molecules.
Language: Английский
Citations
34
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)
Published: Aug. 12, 2023
Abstract An unprecedented Pd‐catalyzed fluorinative bifunctionalization of aziridines and azetidines was successfully developed via regioselective C−C C−F bond cleavage gem‐difluorocyclopropanes, leading to various β,β′‐bisfluorinated amines β,γ‐bisfluorinated amines. This reaction achieved by incorporating a 2‐fluorinated allyl group fluorine atom scissored from gem‐difluorocyclopropane in 100 % economy for the first time. The mechanistic investigations indicated that underwent amine attacking palladium complex generate η 2 ‐coordinated N‐allyl aziridine followed fluoride ligand transfer affording final β‐ γ‐fluorinated
Language: Английский
Citations
31
Green Chemistry, Journal Year: 2023, Volume and Issue: 25(8), P. 3095 - 3102
Published: Jan. 1, 2023
A regiodivergent electrochemical defluorocarboxylation of gem -difluorocyclopropanes is realized, providing access to branched and linear carboxylated monofluorinated alkenes.
Language: Английский
Citations
30
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
17
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
13