Modular Synthesis of Fully‐Substituted and Configuration‐Defined Alkyl Vinyl Ethers Enabled by Dual‐Functional Copper Catalysis DOI
Zhong‐Tao Jiang,

Zhengzhao Chen,

Ying Xia

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(11)

Published: Jan. 10, 2024

Abstract Here we present a modular, chemo‐, regio‐, and stereoselective synthesis of fully‐substituted configuration‐defined alkyl vinyl ethers (AVEs) using simple chemical feedstocks. The distinctive approach involves the chemo‐ regioselective functionalization CF 2 unit in gem ‐difluorinated cyclopropanes with O−H C−H nucleophiles specific order. resulting highly functionalized cyclopropanyl then undergo ring‐opening process to produce AVEs. These AVEs are rarely accessible through conventional methods easily transformable. Mechanistic experiments indicate that success this method relies on use dual‐functional copper catalysis, which is involved both subsequent process.

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

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, 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
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

31
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

17
Modular Synthesis of Fully‐Substituted and Configuration‐Defined Alkyl Vinyl Ethers Enabled by Dual‐Functional Copper Catalysis DOI
Zhong‐Tao Jiang,

Zhengzhao Chen,

Ying Xia

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(11)

Published: Jan. 10, 2024

Here we present a modular, chemo-, regio-, and stereoselective synthesis of fully-substituted configuration-defined alkyl vinyl ethers (AVEs) using simple chemical feedstocks. The distinctive approach involves the chemo- regioselective functionalization CF

Language: Английский

Citations

13
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

13
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

12
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

2
In(OTf)3-Catalyzed (3 + 3) Dipolar Cyclization of Bicyclo[1.1.0]butanes with N-Nucleophilic 1,3-Dipoles: Access to 2,3-Diazabicyclo[3.1.1]heptanes, 2,3-Diazabicyclo[3.1.1]heptenes, and Enantiopure 2-Azabicyclo[3.1.1]heptanes DOI
Jian Zhang,

Jia-Yi Su,

Hanliang Zheng

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17837 - 17849

Published: Nov. 18, 2024

The investigation into the synthesis of azabicyclo[3.1.1]heptanes (azaBCHeps) as bioisosteres to flat aza-aromatics has garnered increasing attention, while it encounters significant challenges. Herein, we have demonstrated In(OTf)3-catalyzed (3 + 3) dipolar cyclization bicyclo[1.1.0]butanes (BCBs) with hydrazones and π-allyl-iridium 1,3-dipoles, engendering a diverse array azaBCHeps. BCBs furnished densely substituted 2,3-diazabicyclo[3.1.1]heptanes 2,3-diazabicyclo[3.1.1]heptenes under nitrogen oxygen atmospheres, respectively. A combination experimental computational investigations lends robust support for proton-transfer-interposed sequential mechanism. More importantly, by integrating In(OTf)3/iridium relay catalysis, enantiopure 2-azabicyclo[3.1.1]heptanes were constructed through aza-π-allyl-iridium in situ generated from N-allyl carbonates. Both methodologies exhibit mild reaction conditions good tolerance various functional groups. Moreover, copious derivatization products highlights utility newly synthesized heterobicyclic motifs versatile building blocks synthetic chemistry.

Language: Английский

Citations

9
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

Citations

14