Palladium-Catalyzed Cross-Coupling of gem-Difluorocyclopropanes with gem-Diborylalkanes for the Synthesis of Boryl-Substituted Fluorinated Alkenes DOI
Ebrahim‐Alkhalil M. A. Ahmed,

Hongchen Zhang,

Wen-Gen Cao

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(50), P. 9020 - 9024

Published: Dec. 8, 2023

This study presents a novel method for the regioselective coupling of gem-difluorinated cyclopropanes with gem-diborylmethane, utilizing Pd-catalyst system. innovative approach enables synthesis 2-fluoroalkenyl monoboronate scaffolds high Z-selectivity. The resulting products undergo further transformations, including oxidation, Suzuki cross-coupling, and trifluoroborylation, all which are achieved good yields. work introduces valuable synthetic pathway to access important fluorinated compounds various applications in organic chemistry.

Language: Английский

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

Zachary P. Cheng,

Yani Luo

et al.

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

33

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

Zhiyao Si

et al.

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

30

Regiodivergent electroreductive defluorinative carboxylation ofgem-difluorocyclopropanes DOI
Bin Zhao,

Zichen Pan,

Jiayu Pan

et al.

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

27

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

Hui Yang,

Yaxin Zeng,

Xiangyu Song

et al.

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

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

et al.

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

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

Binhong Tan,

Hui He

et al.

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

Citations

11

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

Yiliang Gong,

Qing Gu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4287 - 4293

Published: Feb. 25, 2025

Language: Английский

Citations

1

Ligand-controlled regioselective and chemodivergent defluorinative functionalization of gem-difluorocyclopropanes with simple ketones DOI Creative Commons
Leiyang Lv, Huijun Qian, Yangyang Ma

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(47), P. 15511 - 15518

Published: Jan. 1, 2021

Modulating the reaction selectivity is highly attractive and pivotal to rational design of synthetic regimes. The defluorinative functionalization

Language: Английский

Citations

45

Three-component reaction of gem-difluorinated cyclopropanes with alkenes and B2pin2 for the synthesis of monofluoroalkenes DOI
Ayman M. Y. Suliman, Ebrahim‐Alkhalil M. A. Ahmed,

Tian‐Jun Gong

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(52), P. 6400 - 6403

Published: Jan. 1, 2021

Cu/Pd-Catalyzed borylfluoroallylation of alkenes with gem-difluorinated cyclopropanes and B2pin2 was achieved, providing a modular general strategy for the synthesis monofluoroalkenes.

Language: Английский

Citations

41

Recent Advances in Transition-Metal-Catalyzed Cross-Coupling Reactions of gem-Difluorinated Cyclopropanes DOI
Ying Xia,

Yulei Zhu,

Yaxin Zeng

et al.

Synlett, Journal Year: 2022, Volume and Issue: 34(01), P. 1 - 13

Published: July 28, 2022

Abstract As a special class of cyclopropanes, gem-difluorinated cyclopropanes have many fascinating properties as result the gem-difluoro substitution; thus, their reactions received much attention from synthetic chemistry community. Recently, gradually emerged type novel and unique fluorinated allylic synthon in cross-coupling for synthesis monofluoroalkenes. Herein, we briefly summarize recent advances transition-metal-catalyzed cyclopropanes. 1 Introduction 2 Palladium-Catalyzed Reactions with Linear Selectivity 3 Branched 4 Other Metal-Catalyzed 5 Conclusions

Language: Английский

Citations

38