Cross‐ and Multi‐Coupling Reactions Using Monofluoroalkanes DOI Creative Commons
Takanori Iwasaki, Nobuaki Kambe

The Chemical Record, Journal Year: 2023, Volume and Issue: 23(9)

Published: April 18, 2023

Abstract Carbon‐fluorine bonds are stable and have demonstrated sluggishness against various chemical manipulations. However, selective transformations of C−F can be achieved by developing appropriate conditions as useful synthetic methods in organic chemistry. This review focuses on C−C bond formation at monofluorinated sp 3 ‐hybridized carbons via cleavage, including cross‐coupling multi‐component coupling reactions. The cleavage mechanisms the carbon centers primarily categorized into three types: Lewis acids promoted F atom elimination to generate carbocation intermediates; nucleophilic substitution with metal or nucleophiles supported activation coordination acids; a single electron transfer. characteristic features alkyl fluorides, comparison other (pseudo)halides promising electrophilic counterparts, also discussed.

Language: Английский

Transition metal nanoparticles as nanocatalysts for Suzuki, Heck and Sonogashira cross-coupling reactions DOI Creative Commons
Muhammad Ashraf,

Muhammad Sohail Ahmad,

Yusuke Inomata

et al.

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 476, P. 214928 - 214928

Published: Nov. 11, 2022

Language: Английский

Citations

82
Photocatalytic Three-Component Reductive Coupling Synthesis of gem-Difluorohomoallyl Secondary Amines DOI

Bingbing Feng,

Meifang Tang,

Rui Xiao

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

gem-Difluorohomoallyl amines, an important class of gem-difluoroalkenes, are prevalent moieties in many bioactive compounds. However, limited methods suitable for the synthesis this type compound containing secondary amines. Here, we display a photocatalytic multicomponent protocol gem-difluoroalkenes which makes use readily available materials: arylamines, alkyl aldehydes, and α-trifluoromethyl alkenes. Moreover, ketones amines also substrates. Preliminary mechanistic experiments indicate that key α-amino radical was involved, generated from reduction situ-formed imines (or iminium ions) by reduced photocatalyst. Subsequent addition to alkenes β-F elimination deliver desired products.

Language: Английский

Citations

2
Recent Advances in C-F Bond Cleavage Enabled by Visible Light Photoredox Catalysis DOI Creative Commons
Lei Zhou

Molecules, Journal Year: 2021, Volume and Issue: 26(22), P. 7051 - 7051

Published: Nov. 22, 2021

The creation of new bonds via C-F bond cleavage readily available per- or oligofluorinated compounds has received growing interest. Using such a strategy, myriad valuable partially fluorinated products can be prepared, which otherwise are difficult to make by the conventional formation methods. Visible light photoredox catalysis been proven as an important and powerful tool for defluorinative reactions due its mild, easy handle, environmentally benign characteristics. Compared classical activation that proceeds two-electron processes, radicals key intermediates using visible catalysis, providing modes bonds. In this review, summary light-promoted since 2018 was presented. contents were classified fluorosubstrates, including polyfluorinated arenes, gem-difluoroalkenes, trifluoromethyl alkenes. An emphasis is placed on discussion mechanisms limitations these reactions. Finally, my personal perspective future development rapidly emerging field provided.

Language: Английский

Citations

57
The Directing Group: A Tool for Efficient and Selective C–F Bond Activation DOI
Amrita Das, Naoto Chatani

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(21), P. 12915 - 12930

Published: Oct. 8, 2021

C–F bond activation is currently considered to be "a hot topic" in many different but interconnected fields of research, due its inherent inertness and unique properties. While considerable progress has been made this particular field activating strong bonds, such as the bond, continues a challenge. Because polyfluorinated compounds are commercially available, functionalization bonds extensively studied for preparing partially fluorinated compounds, some which biologically active used functionalized materials. However, chemo- regioselective methods still required prepare useful compounds. In addition, new strategy less reactive monofluorinated remains need. Directed strategies have C–H chemistry achieve high efficiency well regioselectivity. On other hand, directed that applicable various unreactive C–O, C–N, C–F, others needed, compared with activation. Review, we focus on inert bonds.

Language: Английский

Citations

50
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
Enantioselective nickel-catalyzed Mizoroki–Heck cyclizations of amide electrophiles DOI Creative Commons
Ana S. Bulger, Daniel J. Nasrallah, Arismel Tena Meza

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(7), P. 2593 - 2600

Published: Jan. 1, 2024

The first asymmetric amide cross-couplings that rely on C–N bond activation using transition metal catalysis are reported. study establishes a new avenue in chemistry.

Language: Английский

Citations

7
Divergent Transformations of Aromatic Esters: Decarbonylative Coupling, Ester Dance, Aryl Exchange, and Deoxygenative Coupling DOI Creative Commons
Masayuki Kubo, Junichiro Yamaguchi

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(12), P. 1747 - 1760

Published: May 31, 2024

ConspectusAromatic esters are cost-effective, versatile, and commonly used scaffolds that readily synthesized or encountered as synthetic intermediates. While most conventional reactions involving these nucleophilic acyl substitutions 1,2-nucleophilic additions─where a nucleophile attacks the carbonyl group, decarbonylative transformations offer an alternative pathway by using group leaving group. This transition-metal-catalyzed process typically begins with oxidative addition of C(acyl)–O bond to metal. Subsequently, reaction involves migration CO metal center, nucleophile, reductive elimination yield final product. Pioneering work Yamamoto on nickel complexes development (such Mizoroki–Heck-type olefination) aromatic carboxylic anhydrides catalyzed palladium were conducted de Vries Stephan. Furthermore, reports have surfaced hydrogenation pyridyl methyl Murai ruthenium catalysts well nitro phenyl Gooßen under catalysis. Our has been at forefront developing C–H arylations 1,3-azoles aryl boronic acids catalysts. The key this is use esters, which easy synthesize, stabilize, handle, allowing bond; nickel, facilitates suitable bidentate phosphine ligands can stabilize intermediate. By modification nucleophiles, effectively utilized electrophiles in cross-coupling reactions, encouraging nucleophiles among researchers. Account summarizes our advancements for coupling particularly highlighting utilization diverse such alkenylation, intramolecular etherification, α-arylation ketones, arylation, methylation, arylation dibenzofuran synthesis, along cyanation coupling. We also delve into types distinct from typical including ester dance ring exchanges, deoxygenative transformations, focusing complex. For example, hypothesized undergo 1,2-translocation starting complex, leading sequence ortho-deprotonation/decarbonylation, followed protonation, carbonylation, elimination. exchange likely different In coupling, complex engages forming intermediate undergoes presence appropriate reducing agent. These methodologies poised captivate interest chemists offering unconventional emerging approaches transforming esters. Moreover, we demonstrated potential transform available basic chemicals new compounds through organic synthesis.

Language: Английский

Citations

6
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

Citations

28
Synergistic Pd/Cu-catalyzed enantioselective Csp2–F bond alkylation of fluoro-1,3-dienes with aldimine esters DOI Creative Commons
Huimin Yu, Qinglong Zhang, Weiwei Zi

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 5, 2022

Due to high bond dissociation energies of Csp2-F bonds, using fluorinated compounds in Csp2-Csp3 cross-coupling is difficult. Here the authors report a protocol for enantioselective coupling dienyl fluorides with aldimine esters, enabled by synergistic copper and palladium catalysis. This reaction represents first example asymmetric involving an inert provides expeditious access chiral α-alkenyl α-amino acids enantioselectivity. Control experiments suggest that activation occurs through pathway PdH migratory insertion subsequent allylic defluorination, rather than direct oxidative addition Pd(0). The detailed mechanism further investigated DFT calculation enantioselectivity rationalized.

Language: Английский

Citations

26
Cationic Rhodium(I) Tetrafluoroborate Catalyzed Intramolecular Carbofluorination of Alkenes via Acyl Fluoride C−F Bond Activation** DOI
Tomoki Yoshida,

Masaya Ohta,

Tomoya Emmei

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 31, 2023

The C-F bond of acyl fluorides can be cleaved and added across tethered alkenes in the presence a cationic rhodium(I) tetrafluoroborate catalyst. This 1,2-carbofluorination reaction offers powerful method for synthesis tertiary alkyl fluoride derivatives with an atom economy 100 %. Mechanistic studies indicate that concerted action rhodium cation anion is key success this catalytic cleavage formation bonds controlled manner.

Language: Английский

Citations

15