BF3-Catalyzed Intramolecular Fluorocarbamoylation of Alkynes via Halide Recycling DOI Creative Commons
E. Ali McKnight, Ramon Arora, Ekadashi Pradhan

et al.

Published: April 19, 2023

A BF3-catalyzed atom-economical fluorocarbamoylation reaction of alkyne-tethered carbamoyl fluorides is reported. The catalyst acts as both a fluoride source and Lewis acid activator, enabling the formal insertion alkynes into strong C–F bonds through halide recycling mechanism. developed method provides access to 3-(fluoromethylene)oxindoles γ-lactams with excellent stereoselectivity, including fluorinated derivatives known protein kinase inhibitors. Experimental computational studies support stepwise mechanism for involving turnover-limiting cyclization step, followed by internal transfer from BF3-coordinated adduct. For methylene oxindoles, thermodynamically driven Z-E isomerization facilitated transition state aromatic character. In contrast, this stabilization not relevant γ-lactams, resulting in higher barrier exclusive formation kinetic Z-isomer.

Language: Английский

BF3-Catalyzed Intramolecular Fluorocarbamoylation of Alkynes via Halide Recycling DOI
E. Ali McKnight, Ramon Arora, Ekadashi Pradhan

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 11012 - 11018

Published: May 12, 2023

A BF3-catalyzed atom-economical fluorocarbamoylation reaction of alkyne-tethered carbamoyl fluorides is reported. The catalyst acts as both a fluoride source and Lewis acid activator, thereby enabling the formal insertion alkynes into strong C-F bonds through halide recycling mechanism. developed method provides access to 3-(fluoromethylene) oxindoles γ-lactams with excellent stereoselectivity, including fluorinated derivatives known protein kinase inhibitors. Experimental computational studies support stepwise mechanism for involving turnover-limiting cyclization step, followed by internal transfer from BF3-coordinated adduct. For methylene oxindoles, thermodynamically driven Z-E isomerization facilitated transition state aromatic character. In contrast, this stabilization not relevant γ-lactams, which results in higher barrier exclusive formation Z-isomer.

Language: Английский

Citations

31
Photoinduced N-Heterocyclic Nitrenium-Catalyzed Single Electron Reduction of Acyl Fluorides for Phenanthridine Synthesis DOI
Lei Bao, Zhixiang Wang, Xiang‐Yu Chen

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(3), P. 565 - 568

Published: Jan. 13, 2023

Acyl fluorides are versatile reagents in organic synthesis. However, there is no precedent to employ acyl as radical precursors. We herein report an N-heterocyclic nitrenium iodide salt-catalyzed photoreduction of produce radicals, which could react with 2-isocyanobiaryls afford various carbonyl phenanthridines.

Language: Английский

Citations

23
Taking Olefin Metathesis to the Limit: Stereocontrolled Synthesis of Trisubstituted Alkenes DOI
Amir H. Hoveyda, Can Qin,

Xin Zhi Sui

et al.

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(18), P. 2426 - 2446

Published: Aug. 29, 2023

ConspectusIn this Account, we share the story of development catalytic olefin metathesis processes that efficiently deliver a wide range acyclic and macrocyclic E- or Z-trisubstituted alkenes. The tale starts with us unveiling, in collaboration Richard Schrock his team, blueprint 2009 for design kinetically controlled Z-selective reactions. This paved way Mo-, W-, Ru-based catalysts strategies synthesizing countless linear Z-olefins. Six years later, 2015, found abundant Z-alkene feedstocks, such as oleic acid, can be directly transformed to high-value more difficult-to-access alkenes through cross-metathesis reaction promoted by Ru-catechothiolate complex had developed; approach, later coined stereoretentive metathesis, was extended synthesis E-alkenes.It all about disubstituted until when 2017 addressed challenge accessing stereodefined Z- E-trisubstituted alkenes, key medicine materials research. These transformations most effectively catalyzed Mo monoaryloxides pyrrolide (MAP) chloride (MAC) complexes. A central aspect advance is merging which delivered trisubstituted alkenyl fluorides, chlorides, bromides cross-coupling. used various combinations, thereby enabling access assorted alkene. Ensuing work led emergence other involving substrates purchased high stereoisomeric purity, notably Z-trihalo Trisubstituted olefins, Z E, bearing chemoselectively stereoretentively alterable F,Cl-terminus B(pin),Cl-terminus may, thus, easily reliably synthesized. Methods preparation bromide regioisomers α,β-unsaturated carboxylic thiol esters, nitriles, acid fluorides followed, along ring-closing reactions afford olefins. E-Macrocyclic including those contain little no entropic support cyclization (minimally functionalized) and/or are disfavored under substrate-controlled conditions, now utility latest chapter history has been highlighted applications several biologically active compounds, well their analogues, marked one site-specifically incorporated fluorine atoms but higher energy otherwise unobtainable conformers.The investigations discussed here, represent every method reported thus far preparing olefin, underscore inimitable power Mo-based catalysts. Account also showcases variety mechanistic attributes─some first time, each instrumental solving problem. Extensive knowledge nuances will needed if address successfully next challenging problem, namely, may synthesize tetrasubstituted especially readily modifiable, purity.

Language: Английский

Citations

20
Mechanochemical Deoxyfluorination of Carboxylic Acids to Acyl Fluorides and Successive Mechanochemical Amide Bond Formation DOI

Zhengyu Zhao,

Sota Ikawa,

Soichiro Mori

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(9), P. 3565 - 3574

Published: Feb. 16, 2024

Diverse methods have been reported for the synthesis of acyl fluorides; however, an environmentally benign method fluorides remains underdeveloped. In this study, we developed solvent-free mechanochemical deoxyfluorination carboxylic acids to mediated by 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine (TFEDMA) using a ball mill. This facilitated high product yields in short reaction times even sterically challenged acids. We also realized coupling and amines as well TFEDMA-mediated direct with via sequential one-pot deoxyfluorination/coupling pathway. Furthermore, protocol was expanded include peptide synthesis. The efficiency protocol, terms speed, characteristics, favorable E-factor, aligns requirements current environmental policies.

Language: Английский

Citations

8
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
C−F Bond Insertion: An Emerging Strategy for Constructing Fluorinated Molecules DOI Creative Commons
Arushi Garg, Alex Haswell, Matthew N. Hopkinson

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(20)

Published: Jan. 25, 2024

C-F Insertion reactions, where an organic fragment formally inserts into a carbon-fluorine bond in substrate, are highly attractive, yet largely unexplored, methods to prepare valuable fluorinated molecules. The inherent strength of bonds and the resulting need for large thermodynamic driving force initiate cleavage often leads sequestering released fluoride unreactive by-product. Recently, however, several groups have succeeded overcoming this challenge, opening up study insertion as efficient atom-economical approach compounds. In article, recent breakthroughs discussed focusing on key conceptual advances that allowed both subsequent incorporation product.

Language: Английский

Citations

6
Unlocking the Power of Acyl Fluorides: A Comprehensive Guide to Synthesis and Properties DOI
Clémence Bonnefoy, Adrien Gallego, Clément Delobel

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(18)

Published: March 6, 2024

Abstract Acyl fluorides have emerged as versatile reagents in various synthetic endeavors, offering a range of advantages over their counterparts, acyl chlorides. This study delves into the properties and reactivity fluorides, particularly reaction with amines alcohols, to elucidate distinct characteristics. We also introduce facile practical synthesis from stable solution CF 3 O − salt. Additionally, we establish an efficient one‐pot process for direct preparation amides or esters corresponding acids showcasing remarkable efficiency these transformations.

Language: Английский

Citations

6
1,2-Diacylation of Alkynes Using Acyl Fluorides and Acylsilanes by P(III)/P(V) Catalysis DOI
Hayato Fujimoto,

Shisato Yamamura,

Momoka Kusano

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(2), P. 336 - 340

Published: Jan. 5, 2023

We report herein the phosphine-catalyzed 1,2-diacylation of alkynes using acyl fluorides and acylsilanes as sources. The key to success reaction is a formal oxidative addition-ligand metathesis-reductive elimination cycle based on phosphine redox catalysis, which allows for installation two different groups into an alkyne in regioselective manner.

Language: Английский

Citations

13
Recent Advances in the Synthesis and Transformation of Carbamoyl Fluorides, Fluoroformates, and Their Analogues DOI
Lei Liu, Yu‐Cheng Gu, Cheng‐Pan Zhang

et al.

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

Published: April 26, 2023

Abstract Carbamoyl fluorides, fluoroformates, and their analogues are a class of important compounds have been evidenced as versatile building blocks for the preparation useful molecules in organic chemistry. While major achievements were made synthesis carbamoyl last half 20 th century, an increasing number reports focused on using O/S/Se=CF 2 species or equivalents fluorocarbonylation reagents direct construction these from parent heteroatom‐nucleophiles recent years. This review mainly summarizes advances typical application by halide exchanges reactions since 1980.

Language: Английский

Citations

11
Nickel-Catalyzed Decarbonylative Reductive Alkylation of Aroyl Fluorides with Alkyl Bromides DOI
Qiang Chen,

Jingwen You,

Tian Tian

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(50), P. 9259 - 9263

Published: Dec. 14, 2022

This paper describes the nickel-catalyzed reductive alkylation of aroyl fluorides with alkyl bromides in a decarbonylative manner. In this reaction, various functional groups are well tolerated and C(sp2)-C(sp3) bond can be constructed directly without use organometallic reagents. The present reaction is cross-electrophile coupling via radical pathway, affording corresponding alkylarenes moderate to good yields.

Language: Английский

Citations

16