Aromatic nitrogen scanning by ipso -selective nitrene internalization

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

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Catalytic Diversification of gem‐Difluorocyclopropanes: Recent Advances and Challenges

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

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Chemo‐, Stereo‐ and Regioselective Fluoroallylation/Annulation of Hydrazones with gem‐Difluorocyclopropanes via Tunable Palladium/NHC Catalysis

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

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Rhodium‐Catalyzed Regio‐ and Diastereoselective [3+2] Cycloaddition of gem‐Difluorinated Cyclopropanes with Internal Olefins

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

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Pd/IPr^BIDEA-Catalyzed Hydrodefluorination of gem-Difluorocyclopropanes: Regioselective Synthesis of Terminal Fluoroalkenes

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

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Palladium‐Catalyzed Fluorinative Bifunctionalization of Aziridines and Azetidines with gem‐Difluorocyclopropanes

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

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Regiodivergent electroreductive defluorinative carboxylation ofgem-difluorocyclopropanes

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

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Rhodium‐Catalyzed Enantio‐ and Regioselective Allylation of Indoles with gem‐Difluorinated Cyclopropanes

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

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Selectivity in Rh-catalysis with gem-difluorinated cyclopropanes

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

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Enantioselective Tsuji‐Trost α‐Fluoroallylation of Amino Acid Esters with Gem‐Difluorinated Cyclopropanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: Feb. 27, 2024

A novel enantioselective Tsuji-Trost-type cross coupling reaction between gem-difluorinated cyclopropanes and N-unprotected amino acid esters enabled by synergistic Pd/Ni/chiral aldehyde catalysis is presented herein. This transformation streamlined the diversity-oriented synthesis (DOS) of optically active α-quaternary α-amino bearing a linear 2-fluoroallylic motif, which served as an appealing platform for construction other valuable enantioenriched compounds. The key intermediates were confirmed HRMS detection, while DFT calculations revealed that excellent enantioselectivity was attributed to stabilizing non-covalent interactions Pd(II)-π-fluoroallyl species Ni(II)-Schiff base complex.

Language: Английский

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