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

Hui Yang,

Yaxin Zeng,

Xiangyu Song

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(22)

Опубликована: Март 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.

Язык: Английский

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

Hieu D. Nguyen,

Leiyang Lv

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)

Опубликована: Апрель 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.

Язык: Английский

Процитировано

36

Pd/IPrBIDEA-Catalyzed Hydrodefluorination of gem-Difluorocyclopropanes: Regioselective Synthesis of Terminal Fluoroalkenes DOI
Huijun Qian,

Zachary P. Cheng,

Yani Luo

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 24 - 32

Опубликована: Окт. 13, 2023

Developing new strategies to enable chemo- and regioselective reductions is an important topic in chemical research. Herein, efficient Pd/IPr

Язык: Английский

Процитировано

35

Rhodium‐Catalyzed Regio‐ and Diastereoselective [3+2] Cycloaddition of gem‐Difluorinated Cyclopropanes with Internal Olefins DOI
Yaxin Zeng, Ying Xia

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)

Опубликована: Июнь 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.

Язык: Английский

Процитировано

34

Palladium‐Catalyzed Fluorinative Bifunctionalization of Aziridines and Azetidines with gem‐Difluorocyclopropanes DOI
Dong‐Dong Li, Chaoren Shen,

Zhiyao Si

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(42)

Опубликована: Авг. 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

Язык: Английский

Процитировано

31

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

Hui Yang,

Yaxin Zeng,

Xiangyu Song

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(22)

Опубликована: Март 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.

Язык: Английский

Процитировано

17

Selectivity in Rh-catalysis with gem-difluorinated cyclopropanes DOI
Yaxin Zeng, Zhong‐Tao Jiang, Ying Xia

и другие.

Chemical Communications, Год журнала: 2024, Номер 60(28), С. 3764 - 3773

Опубликована: Янв. 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.

Язык: Английский

Процитировано

13

Enantioselective Tsuji‐Trost α‐Fluoroallylation of Amino Acid Esters with Gem‐Difluorinated Cyclopropanes DOI
Zheng Su,

Binhong Tan,

Hui He

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Фев. 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.

Язык: Английский

Процитировано

12

Observation of unusual outer-sphere mechanism using simple alkenes as nucleophiles in allylation chemistry DOI Creative Commons
Yaxin Zeng, Han Gao, Zhong‐Tao Jiang

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 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.

Язык: Английский

Процитировано

12

Rhodium-Catalyzed Asymmetric Allylic Dearomatization of β-Naphthols with gem-Difluorinated Cyclopropanes DOI
Ziqi Yang,

Yiliang Gong,

Qing Gu

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4287 - 4293

Опубликована: Фев. 25, 2025

Язык: Английский

Процитировано

2

Synthesis of α-Difluoromethylene Ethers via Photoredox-Induced Hyperconjugative Ring Opening of gem-Difluorocyclopropanes DOI

Yu‐Rou Zhao,

Zhiyong Ma, Le Liu

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(6), С. 3787 - 3793

Опубликована: Фев. 24, 2023

Fluorinated compounds have found widespread applications in pharmaceuticals, agrochemicals, and materials science. Precise construction of α-difluoromethylene ether (CF2-O) moiety organic molecules is high demand. Herein, a visible light-promoted reaction protocol for the synthesis from gem-difluorocyclopropane described. The key ring-opening step induced by hyperconjugative interaction cyclopropane with photo-oxidized aromatic rings. This easy scale-up, products bearing synthetic handle enable their further manipulation.

Язык: Английский

Процитировано

17