Efficient Access to Extended Yagupolskii–Umemoto‐Type Reagents: Triflic Acid Catalyzed Intramolecular Cyclization of <i>ortho</i>‐Ethynylaryltrifluoromethylsulfanes

Matsnev, Andrej V.; Noritake, Shun; Nomura, Y.; Tokunaga, Etsuko; Nakamura, Shuichi; Shibata, Norio

doi:10.1002/anie.200905225

Cited by 113 publications

(11 citation statements)

References 50 publications

(24 reference statements)

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“…[1][2][3][4][5] Indeed, the appropriate introductiono fafluorine atom or a fluorinated group can drastically affect the biological and physical properties of am olecule andi ts physiological behavior with respect to the modeo fa ction and metabolism. [10][11][12][13][14][15][16][17][18][19][20][21][22][23] The introduction of at rifluoromethylg roup in an enantioselective manner is one of the most challengings ynthetic problems. [10][11][12][13][14][15][16][17][18][19][20][21][22][23] The introduction of at rifluoromethylg roup in an enantioselective manner is one of the most challengings ynthetic problems.…”

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confidence: 99%

“…[6][7][8][9] In this context,t he trifluoromethyl motif has generated high interest. [10][11][12][13][14][15][16][17][18][19][20][21][22][23] The introduction of at rifluoromethylg roup in an enantioselective manner is one of the most challengings ynthetic problems. [19][20][21][22][23] Thus,t he non-asymmetrice lectrophilic atrifluoromethylation of b-keto esters has been extensively studied, whereas the asymmetric examples are scarcely documented.…”

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confidence: 99%

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Lanthanum‐Catalyzed Enantioselective Trifluoromethylation by Using an Electrophilic Hypervalent Iodine Reagent

Granados

Rivilla

Cossío

et al. 2019

Chemistry A European J

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Ah ighlye nantioselective catalytic methodf or the synthesis of quaternary a-trifluoromethyl derivatives of 3-oxo estersi sd escribed. The reaction uses lanthanum(III) triflate andc hiral PyBOX-type C 2 -symmetric ligands to generate intermediate La III complexes that incorporate an enolate moiety of the starting 3-oxo ester and the trifluoromethylation transfer reagent. The enantioselectivity of the reactions tems from the efficient blockage of one of the prochiral faces of the La III enolateb yo ne unit of the C 2 -symmetric ligand. Scheme1.Trifluoromethylation of ester 1a with La(OTf) 3 and reagents 3a,b in the presence of chiral ligands L1-3.Figure 2. Fully optimized geometries of cationic intermediates INT3 and INT4,connected by saddle point TS.Bond distances and angles are given in and degree, respectively.See Figure 1c aption for additional details. The origin of the enantioselectivef ormationo ft he C*···CF 3 bondbyb lockage of one of the prochiral faceso ft he La III -enolate of 1b is highlighted.

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Lanthanum‐Catalyzed Enantioselective Trifluoromethylation by Using an Electrophilic Hypervalent Iodine Reagent

Granados

Rivilla

Cossío

et al. 2019

Chemistry A European J

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“…Using 4.0 equiv of Umemoto’s reagent 3b instead of 3a gave the product 2a in 27% yield (Table 1, entry 12). S -(Trifluoromethyl)benzothiophenium salt 3c [24], trifluoromethylsulfoxinium salt 3d [25], and hypervalent iodine(III) CF 3 reagent 3e [26] did not proceed or provided only a trace amount of the desired product 2a under the same reaction conditions (Table 1, entries 13–15). No reaction was observed using Ruppert–Prakash reagent in the presence of Cu under the same conditions (Table 1, entry 16).…”

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confidence: 99%

Regioselective 1,4-trifluoromethylation of α,β-unsaturated ketones via a S-(trifluoromethyl)diphenylsulfonium salts/copper system

Okusu¹,

Sugita²,

Tokunaga³

et al. 2013

Beilstein J. Org. Chem.

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Regioselective conjugate 1,4-trifluoromethylation of α,β-unsaturated ketones by the use of shelf-stable electrophilic trifluoromethylating reagents, S-(trifluoromethyl)diphenylsulfonium salts and copper under mild conditions is described. A wide range of acyclic aryl-aryl-enones and aryl-alkyl-enones were converted into β-trifluoromethylated ketones in low to moderate yields. 2189Scheme 1: Trifluoromethylation of α,β-unsaturated ketones.

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“…Ortho -ethynylaryl- and alkyl-trifluoromethylsulfanes were cyclized under strong acidic conditions with triflic acid to give the corresponding sulfonium salts in 64–94% yields (Scheme 12). It should be noted, that in the presence of gold or copper salts no cyclization occurs [22]. …”

Section: Reviewmentioning

confidence: 99%

“…Reagent 18 was obtained as a 1:1 mixture of diastereoisomers originating from the chirality at the sulfur atom. The trifluoromethylation of a β-ketoester by 18 was then carried out in the presence of DBU to furnish the trifluoromethylated β-ketoester in 43% yield but as a racemate (Scheme 14) [22]. …”

Section: Reviewmentioning

confidence: 99%

Shelf-stable electrophilic trifluoromethylating reagents: A brief historical perspective

Shibata¹,

Matsnev²,

Cahard³

2010

Beilstein J. Org. Chem.

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SummarySince the discovery by Yagupolskii and co-workers that S-trifluoromethyl diarylsulfonium salts are effective for the trifluoromethylation of thiophenolates, the design and synthesis of electrophilic trifluoromethylating reagents have been extensively researched in both academia and industry, due to the significant unique features that trifluoromethylated compounds have in pharmaceuticals, agricultural chemicals, and functional materials. Several effective reagents have been developed by the groups of Yagupolskii, Umemoto, Shreeve, Adachi, Magnier, Togni and Shibata. Due to the high stability and reactivity of these reagents, a series of Umemoto reagents, Togni reagent and Shibata reagent are now commercially available. In this review, we wish to briefly provide a historical perspective of the development of so-called “shelf-stable electrophilic trifluoromethylating reagents”, although this field is in constant development.

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Efficient Access to Extended Yagupolskii–Umemoto‐Type Reagents: Triflic Acid Catalyzed Intramolecular Cyclization of ortho‐Ethynylaryltrifluoromethylsulfanes

Cited by 113 publications

References 50 publications

Lanthanum‐Catalyzed Enantioselective Trifluoromethylation by Using an Electrophilic Hypervalent Iodine Reagent

Lanthanum‐Catalyzed Enantioselective Trifluoromethylation by Using an Electrophilic Hypervalent Iodine Reagent

Regioselective 1,4-trifluoromethylation of α,β-unsaturated ketones via a S-(trifluoromethyl)diphenylsulfonium salts/copper system

Shelf-stable electrophilic trifluoromethylating reagents: A brief historical perspective

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