Recent Advances in C–F Bond Activation of Acyl Fluorides Directed toward Catalytic Transformation by Transition Metals, N-Heterocyclic Carbenes, or Phosphines DOI
Yasushi Nishihara, Tian Tian, Qiang Chen

et al.

Synthesis, Journal Year: 2022, Volume and Issue: 54(17), P. 3667 - 3697

Published: May 6, 2022

Abstract Numerous studies on the activation of carbon–fluorine bonds have been reported in recent years. For example, acyl fluorides utilized as versatile reagents for acylation, arylation, and even fluorination. In this review, we focus compounds with bonds, highlight advances strategies their C–F via transition-metal catalysis, N-heterocyclic carbene (NHCs) organophosphine classical nucleophilic substitution reactions. 1 Introduction 2 Transition-Metal-Mediated Bond Activation 2.1 Acylation (Carbonyl-Retentive) Coupling Reactions 2.2 Decarbonylative 2.3 by Other Transition Metals 3 N-Heterocyclic Carbenes 3.1 NHC-Catalyzed Cycloaddition Acyl Fluorides 3.2 Radical Functionalization 3.3 Nucleophilic Fluorination (Hetero)aromatics 4 Phosphines 4.1 Phosphine-Catalyzed Direct 4.2 Indirect 5 Classical Substitution 6 Miscellaneous Examples 7 Summary Perspective

Language: Английский

Diastereoselective Synthesis of Monofluorocyclohexenes through Photocatalyzed Cascade Cyclization of gem‐Difluoroalkenes and α,β‐Unsaturated Carbonyl Compounds DOI
Zhengyu Li, Yizhi Zhang, Yunxiao Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 16, 2023

Monofluoroalkenes are nonhydrolyzable mimetics of amides. Previous work focused on the synthesis non-cyclic monofluoroalkenes. However, diastereoselective monofluorocyclohexenes from substrates is challenging. Herein, we report first photocatalyzed cascade cyclization reactions readily available α,β-unsaturated carbonyl compounds and gem-difluoroalkenes for highly functionalized monofluorocyclohexenes. The reaction shows broad substrate scope with high diastereoselectivity (>30 examples, up to 86 % yield, >20 : 1 dr). post-reaction transformations products demonstrate synthetic potential this methodology.

Language: Английский

Citations

24
Pd/Cu‐Catalyzed Defluorinative Carbonylative Coupling of Aryl Iodides and gem‐Difluoroalkenes: Efficient Synthesis of α‐Fluorochalcones DOI
Fu‐Peng Wu, Yang Yuan, Jiawang Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(16), P. 8818 - 8822

Published: Feb. 5, 2021

Abstract An unprecedented and challenging defluorinative carbonylation was achieved. Enabled by a Pd/Cu cooperative catalyst system, the first example of carbonylative coupling has been established. With gem ‐difluoroalkenes aryl iodides as substrates, this methodology offers flexible facile access to privileged α‐fluorochalcones under mild reaction conditions in moderate‐to‐excellent yields. Mechanistic studies indicated transmetalation between palladium copper intermediates crucial step catalytic cycle.

Language: Английский

Citations

53
Asymmetric Synthesis of 2,2‐Difluorotetrahydrofurans through Palladium‐Catalyzed Formal [3+2] Cycloaddition DOI
Jun Liu,

Longhui Yu,

Changwu Zheng

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(44), P. 23641 - 23645

Published: Sept. 8, 2021

The asymmetric synthesis of 2,2-difluorinated tetrahydrofurans was accomplished via enantioselective formal [3+2] cycloaddition catalyzed by palladium. reaction between gem-difluoroalkenes and racemic vinyl epoxides or vinylethylene carbonates resulted in the formation enantioenriched 2,2-difluorotetrahydrofurans with an enantioselectivity up to 98 %. Notably, used readily available (R)-BINAP as ligand at a low loading yielded wide variety difluorinated products moderate high yields. Both chiral diastereomers could be obtained single sequence.

Language: Английский

Citations

49
Solvent‐Switched Oxidation Selectivities with O2: Controlled Synthesis of α‐Difluoro(thio)methylated Alcohols and Ketones DOI
Chi Liu, Chuanle Zhu, Yingying Cai

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(21), P. 12038 - 12045

Published: March 11, 2021

Abstract The solvent‐switched hydroxylation and oxygenation of α‐difluoro(thio)methylated carbanions with molecular oxygen under mild conditions are reported. This strategy tames the redox reactions in situ generated hydroperoxy difluoromethylsulfides, which solvent‐bonding can alter their reactivity switch oxidation selectivities. These controllable three‐component gem ‐difluoroalkenes, thiols afford various useful alcohols ketones high yields. Significantly, this protocol has been applied synthesis different bioactive molecules. Mechanism studies enable detection difluoromethylsulfide intermediates exclude thiol‐based radical pathway.

Language: Английский

Citations

48
Recent Advances in Transition‐metal‐catalyzed C−C Bond Formation via C(sp2)−F Bond Cleavage DOI

Liyan Fu,

Qiang Chen, Yasushi Nishihara

et al.

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(12), P. 3394 - 3410

Published: April 14, 2021

Abstract The activation of a carbon‐fluorine bond is one the most challenging topics in modern synthetic organic chemistry due to their low reactivity compared other carbon‐halogen bonds. In this review, we present recent developments since 2015 on cross‐coupling reactions that form C−C bonds via cleavage C( sp 2 )−F Not only conventional bonds, but also decarbonylative or carbonyl‐retentive C(acyl)−F will be introduced. This paper mainly describes new protocols for formation )−C( 3 ), and ) transition‐metal‐catalyzed

Language: Английский

Citations

47
1,3-Difunctionalization of alkenes: state-of-the-art and future challenges DOI
Dongkai Wang, Long Li,

Qing Xu

et al.

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(24), P. 7037 - 7049

Published: Jan. 1, 2021

This review summarizes the advances in 1,3-difunctionalization of alkenes mediated by Pd-, Ni-, Fe-, and Cu-based catalysts, as well under metal-free conditions, with an emphasis on reaction mechanisms factors governing regioselectivity.

Language: Английский

Citations

46
Defluorinative C–C Bond-Forming Reaction of Trifluoromethyl Alkenes with gem-(Diborylalkyl)lithiums DOI
Haeun Kim,

Yujin Jung,

Seung Hwan Cho

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(14), P. 2705 - 2710

Published: April 5, 2022

We report the transition-metal-free defluorinative C-C bond-forming reaction of trifluoromethyl alkenes with gem-(diborylalkyl)lithiums. This synthetic strategy provides access to a variety 4,4-difluoro homoallylic diboronate esters, which serve as versatile intermediates in efficient preparation valuable gem-difluoroalkene derivatives. Further modifications are conducted demonstrate utility obtained esters.

Language: Английский

Citations

30
Nickel-Catalyzed Stereoselective Cascade C–F Functionalizations of gem-Difluoroalkenes DOI
Xiaowei Li, Yuxiu Li, Zemin Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 2135 - 2141

Published: Jan. 24, 2023

The activation and functionalization of C–F bonds for the construction C–C C–X have drawn significant research attention in recent years. However, chemo- stereoselective control dual bond gem-difluoroalkenes remains a formidable challenge. Herein, Ni-catalyzed reductive cross-coupling with alkenyl-electrophiles D2O that allowed generation C(sp2)–C(sp2) C(sp2)–D one pot by successive defluorination is described. This methodology offers facile access to various deuterated 1,3-dienes broad functional group compatibility (E)-selectivity under mild conditions. Preliminary mechanistic studies indicate α-alkenyl-substituted monofluoroalkenes might be intermediates this protocol.

Language: Английский

Citations

18
Nickel-Catalyzed Cross-Electrophile Ring Opening/gem-Difluoroallylation of Aziridines DOI
Wei Tang, Pei Fan

Organic Letters, Journal Year: 2023, Volume and Issue: 25(31), P. 5756 - 5761

Published: July 28, 2023

Herein we report a nickel-catalyzed regioselective cross-electrophile ring opening reaction of sulfonyl-protected aziridines with trifluoromethyl-substituted alkenes as the gem-difluoroallylating agents, providing new and efficient entry to prepare gem-difluorobishomoallylic sulfonamides. Moreover, scaffold 6-fluoro-1,2,3,4-tetrahydropyridine can be constructed starting from products via NaH-mediated intramolecular defluorinative nucleophilic vinylic substitution.

Language: Английский

Citations

17
Stereoselective hydrodefluorination of CF3-substituted alkenes and gem-difluoroalkenes by H− DOI
Dachang Bai, Xin Li, Fen Wu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(5), P. 1388 - 1394

Published: Jan. 1, 2024

Zn-catalyzed stereoselective hydrodefluorination of CF 3 -substituted alkenes, gem -difluoroalkenes and polyfluoroarenes by hydride ion addition has been realized through controlled C(sp )–F and/or 2 bonds cleavage.

Language: Английский

Citations

7