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

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

et al.

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
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