Advances in Catalytic Enantioselective Fluorination, Mono-, Di-, and Trifluoromethylation, and Trifluoromethylthiolation Reactions

Yang, Xiaoyu; Wu, Tao; Phipps, Robert J.; Toste, F. Dean

doi:10.1021/cr500277b

Cited by 1,242 publications

(406 citation statements)

References 210 publications

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“…Accordingly, significant progress has been made in the field of fluorination of organic molecules 5–7 . Asymmetric methods that directly construct a C(sp 3 )–F stereocenter have also been achieved through multiple approaches 8 including α-fluorination of enolate or enolate-equivalents 9–11 , fluoro-difunctionalization of olefins 12–14 , and asymmetric addition of nucleophilic fluorides to carbon electrophiles 15–17 . As an alternative approach, the development of a direct, enantioselective fluorination of a C(sp 3 )–H bond via metal-insertion would be highly appealing.…”

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confidence: 99%

Controlling Pd(iv) reductive elimination pathways enables Pd(ii)-catalysed enantioselective C(sp3)−H fluorination

et al. 2018

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The development of a Pd(II)-catalyzed enantioselective fluorination of C(sp3)–H bonds would offer a new approach to making chiral organofluorines. However, such a strategy is particularly challenging because of the difficulty in differentiating prochiral C(sp3)–H bonds through Pd(II)-insertion, as well as the sluggish reductive elimination involving Pd–F bonds. Here, we report the development of a Pd(II)-catalyzed enantioselective C(sp3)–H fluorination using a chiral transient directing group strategy. In this work, a bulky, amino amide transient directing group was developed to control the stereochemistry of C–H insertion step and selectively promote C(sp3)–F reductive elimination pathway from Pd(IV)–F intermediate. Stereochemical analysis revealed that while the desired C(sp3)–F formation proceeds via an inner-sphere pathway with retention of configuration, the undesired C(sp3)–O formation occurs through an SN2-type mechanism. The elucidation of the dual mechanism allows us to rationalize the profound ligand effect on controlling reductive elimination selectivity from high-valent Pd species.

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Controlling Pd(iv) reductive elimination pathways enables Pd(ii)-catalysed enantioselective C(sp3)−H fluorination

et al. 2018

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“…Asymmetric electrophilic reactions have been realized in which the electrophile is associated with a chiral anion responsible for the phase transfer catalyzed process (chiral anion phase-transfer (CAPT) catalysis) [305][306][307]. An example is given with the enantioselective electrophilic fluorination of alkenes developed by Toste and co-workers (Scheme 44) [308,309]. Chiral anion transfer of arenediazonium cations has permitted the enantioselective synthesis of C(3)-diazenated pyrroloindolines in a similar way [310].…”

Section: Asymmetric Ion-pairing Catalysismentioning

confidence: 99%

“…Catalysts 2016, 6, 128 32 of 62 [308,309]. Chiral anion transfer of arenediazonium cations has permitted the enantioselective synthesis of C(3)-diazenated pyrroloindolines in a similar way [310].…”

Section: Asymmetric Ion-pairing Catalysismentioning

confidence: 99%

Organocatalysis: Fundamentals and Comparisons to Metal and Enzyme Catalysis

et al. 2016

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Catalysis fulfills the promise that high-yielding chemical transformations will require little energy and produce no toxic waste. This message is carried by the study of the evolution of molecular catalysis of some of the most important reactions in organic chemistry. After reviewing the conceptual underpinnings of catalysis, we discuss the applications of different catalysts according to the mechanism of the reactions that they catalyze, including acyl group transfers, nucleophilic additions and substitutions, and C-C bond forming reactions that employ umpolung by nucleophilic additions to C=O and C=C double bonds. We highlight the utility of a broad range of organocatalysts other than compounds based on proline, the cinchona alkaloids and binaphthyls, which have been abundantly reviewed elsewhere. The focus is on organocatalysts, although a few examples employing metal complexes and enzymes are also included due to their significance. Classical Brønsted acids have evolved into electrophilic hands, the fingers of which are hydrogen donors (like enzymes) or other electrophilic moieties. Classical Lewis base catalysts have evolved into tridimensional, chiral nucleophiles that are N-(e.g., tertiary amines), P-(e.g., tertiary phosphines) and C-nucleophiles (e.g., N-heterocyclic carbenes). Many efficient organocatalysts bear electrophilic and nucleophilic moieties that interact simultaneously or not with both the electrophilic and nucleophilic reactants. A detailed understanding of the reaction mechanisms permits the design of better catalysts. Their construction represents a molecular science in itself, suggesting that sooner or later chemists will not only imitate Nature but be able to catalyze a much wider range of reactions with high chemo-, regio-, stereo-and enantioselectivity. Man-made organocatalysts are much smaller, cheaper and more stable than enzymes.

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“…[1][2][3] The development of effective method for synthesizing fluorine-containing functional molecules has thus gained widespread significant attention in organic synthesis. [4][5][6][7][8][9][10][11] Direct functionalization of inert C-H bonds [12][13][14][15] is a powerful tool to realize atom- 16) and step-economical 17) synthesis, and fluorine or fluorine-containing small functional groups are successfully introduced with various catalysts and reagents. [4][5][6][7][8][9] More recently, C-H functionalization reactions accompanied by selective C-F bond cleavage of multi-fluorinated coupling partners were explored.…”

mentioning

confidence: 99%

Synthesis of Fluorine-Containing 6-Arylpurine Derivatives <i>via</i> Cp*Co(III)-Catalyzed C–H Bond Activation

et al. 2018

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Advances in Catalytic Enantioselective Fluorination, Mono-, Di-, and Trifluoromethylation, and Trifluoromethylthiolation Reactions

Cited by 1,242 publications

References 210 publications

Controlling Pd(iv) reductive elimination pathways enables Pd(ii)-catalysed enantioselective C(sp3)−H fluorination

Controlling Pd(iv) reductive elimination pathways enables Pd(ii)-catalysed enantioselective C(sp3)−H fluorination

Organocatalysis: Fundamentals and Comparisons to Metal and Enzyme Catalysis

Synthesis of Fluorine-Containing 6-Arylpurine Derivatives <i>via</i> Cp*Co(III)-Catalyzed C–H Bond Activation

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