Organocatalytic Reactions of α-Trifluoromethylated Esters with Terminal Alkenes at Room Temperature

Wang, Qi; Feng, Huijin; Shen, Haiming; Xiao, Ji‐Chang; Gao, Min; Yang, Xianjin; Murahashi, Shun‐Ichi; Chen, Qing‐Yun; Guo, Yong

doi:10.1021/jo402212j

Cited by 18 publications

(9 citation statements)

References 75 publications

(30 reference statements)

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“…Evaluation of the NMR spectra indicate, among repeating units from oxa-Michael and transesterification reactions, 28,29 the presence of Rauhut-Currier derived linkages. 30,31,32 This repeat unit is characterized by peaks at 6.22 and 5.64 ppm in the 1 H-NMR spectrum and at 126.6, 33.0, 27.3 ppm in the 13 C-NMR spectrum of poly4 (see Supporting Information) and its share is with approximately 17-20% higher in polymers prepared at 80 °C (Figure 2). The formation of this repeat unit consumes two equivalents of acrylates and thus, disproportionally decreases the quantity of acrylate groups in relation to alcohol groups.…”

Section: Resultsmentioning

confidence: 99%

“…9,10,11 Accordingly, triarylphosphines are generally less reactive in conjugate additions than trialkylphosphines and often high catalyst loadings of up to 20 mol% and elevated temperatures are necessary to obtain satisfactory conversions. 4,12,13 The low reactivity of arylphosphines can be enhanced by introducing electron donating groups (e.g. -CH3, -OMe, -NMe2) at the aryl moieties.…”

Section: Introductionmentioning

confidence: 99%

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Electron Rich Triarylphosphines as Nucleophilic Catalysts for Oxa-Michael Reactions

Fischer¹,

Renner²,

Boese³

et al. 2021

Preprint

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Herein, we study the activity of methoxysubstituted arylphosphines (4-methoxy-phenyl)diphenylphosphine (MMTPP) and tris(4-trimethoxyphenyl)phosphine (TMTPP) in catalyzing oxa-Michael additions in comparison to commonly used triphenylphosphine (TPP). Acrylonitrile, acryl amide and divinyl sulfone are used as Michael acceptors and propargyl alcohol, allyl alcohol, n-propanol and i-propanol are assessed as Michael donors. In many cases, catalyst loadings of only 1 mol% in respect to the Michael acceptor are sufficient to provide full conversion towards the Michael adduct in 24 h at room temperature. Generally, TMTPP is the most active catalyst in all cases. The experimental activity trend was rationalized by calculating the Michael acceptor affinities of all phosphine – Michael acceptor combinations. Besides this parameter, the acidity of the alcohol has a strong impact on the reaction speed. The oxidation stability of the phosphines was evaluated and electron richest TMTPP was found to be only slightly more sensitive to oxidation than TPP. Finally, the catalysts were employed in the oxa-Michael polymerization of 2-hydroxyethyl acrylate. With TMTPP polymers characterized by number average molar masses of about 1200 g/mol at room temperature are accessible. Polymerizations carried out at 80 °C resulted in macromolecules containing a considerable share of Rauhut-Currier type repeat units and consequently lower molar masses were obtained.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electron Rich Triarylphosphines as Nucleophilic Catalysts for Oxa-Michael Reactions

Fischer¹,

Renner²,

Boese³

et al. 2021

Preprint

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“…23 a The notorious C–F bond cleavage of α-trifluoromethyl carbanions competes with other types of transformations in organic synthesis. 125 These interesting properties of C–F bonds could be partially understood in terms of electrostatic/dipole interactions, which were summarized by O'Hagan. 11 To facilitate the C–F bond cleavage step and its defluorination application on the synthesis of heterocyclic compounds, some general principles for C–F bond activation and utilization are highlighted.…”

Section: Discussionmentioning

confidence: 99%

Multiple-fold C–F bond functionalization for the synthesis of (hetero)cyclic compounds: fluorine as a detachable chemical handle

Ge¹,

Chu²

2022

Org. Chem. Front.

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“…The reaction is mild enough to apply to aldimines having the AcO−, TBDMSO−, or MeS− group. LiCl-catalyzed synthesis of β-amino esters 91 via Mannich reaction Wang et al 211 reported 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (XPhos, a phosphine derivative, 93)-catalyzed Michael addition of α-trifluoromethylated ester (92) with α,β-unsaturated ketone (26) in N,N-dimethyformamide (DMF) under an aerobic atmosphere at room temperature resulting to the generation of a series of γ-substituted α-trifluoromethylated ester derivatives (94) with moderate to good yields (Scheme 34). 210 Scheme 33.…”

Section: Addition Reactionsmentioning

confidence: 99%

Design for carbon–carbon bond forming reactions under ambient conditions

Brahmachari

2016

RSC Adv.

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Carbon-carbon (C-C) bond forms the 'backbone' of nearly every organic molecule, and lies at the heart of the chemical sciences! This transformation has always been one of the most useful and fundamental reactions in the development of organic chemistry. Currently, the concept of 'green chemistry' is globally acclaimed and has already advanced quite significantly to come out as a distinct branch of chemical sciences. Among the principles of 'green chemistry', one principle is dedicated to "design of energy efficiency" -that is to develop synthetic strategies that require less/minimum amount of energy to carry out a specific reaction with optimum productivity. And the most effective way-out to save energy is to develop strategies/protocols that are capable enough to carry out the transformations at ambient temperature and pressure! As part of on-going developments on green synthetic strategies, designing for reactions under ambient conditions coupled with other green aspects is, thus, an area of current choice. This review is aimed to offer an up-to-date development on the design of carbon-carbon bond forming protocols to access a wide variety of organic molecules of topical significance under ambient conditions. The account highlights on the brilliant applications of reaction conditions such as the use of solvents or no solvent, catalysts or no catalyst, and the use of green tools like ball-milling, ultrasonication and visible light in achieving the goal! Design for Carbon Carbon Frameworks at Ambient ConditionsN Me Me Me O O COOH Br Br (Graphic for TOC)

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Organocatalytic Reactions of α-Trifluoromethylated Esters with Terminal Alkenes at Room Temperature

Cited by 18 publications

References 75 publications

Electron Rich Triarylphosphines as Nucleophilic Catalysts for Oxa-Michael Reactions

Electron Rich Triarylphosphines as Nucleophilic Catalysts for Oxa-Michael Reactions

Multiple-fold C–F bond functionalization for the synthesis of (hetero)cyclic compounds: fluorine as a detachable chemical handle

Design for carbon–carbon bond forming reactions under ambient conditions

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