Mesoporous TiO2/Celite‐Supported Hydrolysis/Decarboxylation of Benzyl Meldrum's Acid Derivatives: Application to the Synthesis of Hydrocinnamic Acid Derivatives DOI
Muthiah Suresh,

Anusueya Kumari,

Preet Prakash

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(46)

Published: Dec. 1, 2024

Abstract This study describes a method for transforming benzyl Meldrum's acid (BMA) derivatives into aryl propionic (hydrocinnamic acid) using TiO 2 P25 or Celite surfaces under mild conditions. selective decarboxylation and hydrolysis process is particularly effective enolizable derivatives. A key feature of this transformation its chemooselectivity, with acetylated BMA derivatives, which yield the corresponding acids. The offers several advantages, including compatibility wide range structurally diverse acids, reliance on inexpensive materials, elimination bases neutralizing agents, simplified work‐up procedure.

Language: Английский

Asymmetric photoenzymatic incorporation of fluorinated motifs into olefins DOI
Mao‐Lin Li, Yaru Yuan, Wesley Harrison

et al.

Science, Journal Year: 2024, Volume and Issue: 385(6707), P. 416 - 421

Published: July 25, 2024

Enzymes capable of assimilating fluorinated feedstocks are scarce. This situation poses a challenge for the biosynthesis compounds used in pharmaceuticals, agrochemicals, and materials. We developed photoenzymatic hydrofluoroalkylation that integrates motifs into olefins. The photoinduced promiscuity flavin-dependent ene-reductases enables generation carbon-centered radicals from iodinated fluoroalkanes, which directed by photoenzyme to engage enantioselectively with approach facilitates stereocontrol through interaction between singular unit enzyme, securing high enantioselectivity at β, γ, or δ positions groups enzymatic hydrogen atom transfer-a process is notably challenging conventional chemocatalysis. work advances strategies integrating chemical opens avenues asymmetric synthesis compounds.

Language: Английский

Citations

16
Photodriven Radical Perfluoroalkylation–Thiolation of Unactivated Alkenes Enabled by Electron Donor–Acceptor Complex DOI

Lixin Liu,

Qian Wang, Yuanhua Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2271 - 2275

Published: March 8, 2024

A clean and direct three-component radical 1,2-difunctionalization of various alkenes with perfluoroalkyl iodides thiosulfonates enabled by the electron donor–acceptor complex has been developed under light illumination at room temperature. The approach offers a convenient environmentally friendly route for simultaneous incorporation Csp3–Rf Csp3–S bonds, affording valuable polyfunctionalized alkane derivatives containing fluorine sulfur in satisfactory yields. Consequently, this methodology holds significant value practicality field organic synthesis.

Language: Английский

Citations

7
Highly Enantioselective Decarboxylative Difluoromethylation DOI
Xian Zhao, Chao Wang, Lingfeng Yin

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29297 - 29304

Published: Oct. 15, 2024

Organofluorine molecules that contain difluoromethyl groups (CF2H) at stereogenic centers have gained importance in pharmaceuticals due to the unique ability of CF2H act as lipophilic hydrogen bond donors. Despite their potential, enantioselective installation into readily available starting materials remains a challenging and underdeveloped area. In this study, we report nickel-catalyzed decarboxylative difluoromethylation reaction converts alkyl carboxylic acids difluoromethylated products with exceptional enantioselectivity. This Ni-catalyzed protocol exhibits broad functional group tolerance is applicable for synthesizing fluorinated bioisosteres biologically relevant molecules.

Language: Английский

Citations

3
Monodefluorinative Halogenation of Perfluoroalkyl Ketones via Organophosphorus-Mediated Selective C–F Activation DOI Creative Commons
Ha Eun Kim, Jun‐Ho Choi, Won‐jin Chung

et al.

JACS Au, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Through the prosperity of organofluorine chemistry in modern organic synthesis, perfluorinated compounds are now abundant and widely available. Consequently, these substances become attractive starting materials for production complex, multifunctional fluorinated molecules. However, inherent challenges associated with activation discrimination C–F bonds typically lead to overdefluorination as well functional group incompatibility. To address problems, our utilized a rationally designed organophosphorus reagent that promoted mild selective manipulation single bond trifluoromethyl pentafluoroethyl ketones via an interrupted Perkow-type reaction, which allowed replacement fluorine more labile synthetically versatile congeners such chlorine, bromine, iodine. The resulting α-haloperfluoroketones have two reactive units orthogonal properties would be suitable subsequent structural diversification. DFT calculations identified favorable P–F interaction crucial factor from both thermodynamic kinetic viewpoints.

Language: Английский

Citations

0
Enantioconvergent copper-catalysed difluoromethylation of alkyl halides DOI

Decai Ding,

Lingfeng Yin, Andrew T. Poore

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 25, 2024

Language: Английский

Citations

2
Enantioconvergent Copper-Catalysed Difluoromethylation of Alkyl Halides DOI Creative Commons
Wei Liu,

Decai Ding,

Lingfeng Yin

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 16, 2024

Abstract Stereochemical-controlled hydrogen bond donors play essential roles in the pharmaceutical industry. Consequently, organic molecules that bear difluoromethyl (CF2H) groups at chiral centers are emerging as pivotal components pharmaceuticals due to their distinct hydrogenbonding property. However, a general approach for introducing CF2H an enantioselective manner remained elusive. Here, we show enantioconvergent difluoromethylation of racemic alkyl electrophiles, through radical intermediates, represents new strategy constructing CF2H-containing stereocenters. This is enabled by using copper catalysts bound with diamine ligand bearing electron-deficient phenyl groups, and nucleophilic difluoromethyl-zinc reagent. method allows high-yield conversion diverse range halides into alkyl-CF2H analogs excellent enantioselectivity (up 99% e.e.). Mechanistic studies, supported DFT calculations, revealed route involving asymmetric radicals crucial non-covalent interactions enantio-determining steps.

Language: Английский

Citations

1
Asymmetric Fluorocyclization of Difluoroalkenes with Concomitant Formation of a Trifluoromethyl Group DOI

Chino Igarashi,

Tomoya Mayumi,

Hiromichi Egami

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1723 - 1727

Published: Feb. 21, 2024

Asymmetric electrophilic fluorination of difluoroalkenes remains undeveloped because the poor reactivity with electrophiles. However, such reactions, if feasible, are expected to be useful for synthesis chiral heterocyclic compounds a trifluoromethyl group at stereogenic center. In this Letter, we disclose first example asymmetric fluoroamide cyclization using our dianionic phase-transfer catalyst. This reaction provides unique trifluoromethylated oxazoline derivatives synthetically level.

Language: Английский

Citations

1
Synthesis of Tris(trifluoromethyl)nickelates(II)—Coping with “The C2F5 Problem” DOI Creative Commons

Sascha A. Schäfer,

Rose Jordan, Katharina M. Klupsch

et al.

Inorganics, Journal Year: 2024, Volume and Issue: 12(7), P. 187 - 187

Published: July 5, 2024

When synthesizing the versatile precursors (NMe4)[Ni(CF3)3(MeCN)] we recently encountered problem that marked amounts of C2F5 were incorporated instead CF3 under chosen reaction conditions forming mixed-ligand nickelates [Ni(CF3)x(C2F5)y(MeCN)]− (x + y = 3). We studied three products with 0, 1, or 2, using 19F nuclear magnetic resonance (NMR) spectroscopy and single-crystal X-ray diffraction. able to trace mechanism solve by modifying experimental conditions.

Language: Английский

Citations

0
Mesoporous TiO2/Celite‐Supported Hydrolysis/Decarboxylation of Benzyl Meldrum's Acid Derivatives: Application to the Synthesis of Hydrocinnamic Acid Derivatives DOI
Muthiah Suresh,

Anusueya Kumari,

Preet Prakash

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(46)

Published: Dec. 1, 2024

Abstract This study describes a method for transforming benzyl Meldrum's acid (BMA) derivatives into aryl propionic (hydrocinnamic acid) using TiO 2 P25 or Celite surfaces under mild conditions. selective decarboxylation and hydrolysis process is particularly effective enolizable derivatives. A key feature of this transformation its chemooselectivity, with acetylated BMA derivatives, which yield the corresponding acids. The offers several advantages, including compatibility wide range structurally diverse acids, reliance on inexpensive materials, elimination bases neutralizing agents, simplified work‐up procedure.

Language: Английский

Citations

0