Lanthanide trifluoromethanesulfonates as reusable catalysts: catalytic Friedel-Crafts acylation

Kawada, Atsushi; Mitamura, Shuichi; Kobayashi, Shū

doi:10.1039/c39930001157

Cited by 129 publications

(65 citation statements)

References 7 publications

(2 reference statements)

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“…In addition, it was found that addition cyclopentadiene in THF/H 2 O (9:1) at room temperature to of lithium perchlorate (LiClO 4 ) as a co-catalyst improved give the corresponding adduct in a 93% yield (endo/exo ϭ the yields dramatically. [21] This novel Sc(OTf) 3 -catalyzed 100:0) (Equation 9). FriedelϪCrafts acylation reaction is remarkable and has advantages over the conventional AlCl 3 -promoted reaction.…”

Section: Friedel-crafts Acylation and Friesmentioning

confidence: 99%

Scandium Triflate in Organic Synthesis

1999

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Sc(OTf)3 is a new type of a Lewis acid that is different from typical Lewis acids such as AlCl3, BF3, SnCl4, etc. While most Lewis acids are decomposed or deactivated in the presence of water, Sc(OTf)3 is stable and works as a Lewis acid in water solutions. Many nitrogen‐containing compounds such as imines and hydrazones are also successfully activated by using a small amount of Sc(OTf)3 in both organic and aqueous solvents. In addition, Sc(OTf)3 can be recovered after reactions are completed and can be reused. While lanthanide triflates [Ln(OTf)3] have similar properties, the catalytic activity of Sc(OTf)3 is higher than that of Ln(OTf)3 in several cases.

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Section: Friedel-crafts Acylation and Friesmentioning

confidence: 99%

Scandium Triflate in Organic Synthesis

1999

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“…[166][167][168][169][170][171][172] Rareearth triflates and especially scandium(III) triflate have been widely explored as Lewis acids to mediate different types of organic reactions, mainly thanks to the pioneering work by Kobayashi. [172][173][174][175][176][177] Major advantages of these rare-earth salts are that they are water-tolerant Lewis acids (in contrast to strong Lewis acids like AlCl 3 ) and that catalytic amounts rather than stoichiometric amounts can be used in many cases. Although the rare-earth salts have to compete in Lewis acid chemistry with other metal salts like indium(III), [178][179][180] gallium(III), 181,182 and bismuth(III) salts, 183-186 they still remain popular reagents for organic synthesis.…”

Section: Lanthanide-mediated Organic Reactionsmentioning

confidence: 99%

Lanthanides and Actinides in Ionic Liquids

2007

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Koen Binnemans was born in Geel, Belgium, in 1970. He obtained his M. Sc. degree (1992) and Ph.D. degree (1996) in Chemistry at the Catholic University of Leuven, under the direction of Prof. C. Go ¨rller-Walrand. In the period 1999−2005, he was a postdoctoral fellow of the Fund for Scientific Research Flanders (Belgium). He did postdoctoral work with Prof. Jacques Lucas (Rennes, France) and Prof. Duncan W. Bruce (Exeter, U.K.). In 2000, he received the first ERES Junior Award (ERES, European Rare-Earth and Actinide Society). From 2002 until 2005, he was (parttime) associate professor. Presently, he is professor of chemistry at the Catholic University of Leuven. His current research interests are metalcontaining liquid crystals (metallomesogens), lanthanide-mediated organic reactions, lanthanide spectroscopy, supramolecular coordination chemistry, and ionic liquids.

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“…During the course of our investigations about Friedel-Crafts acylation, we found that acetyl perchlorate, the mixed anhydride of acetic acid and perchloric acid, which acts as an active acylating agent is generated from acetic anhydride and lithium perchlorate in the presence of RE(OTf) 3 . [46][47][48][49] Based on this consideration, the efficient generation of acyl nitrate is expected between an inorganic nitrate and carboxylic anhydride in the presence of RE(OTf) 3 , and we tried to examine the nitration of aromatic compounds using the RE(OTf) 3 -carboxylic anhydride-inorganic nitrate system. …”

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confidence: 99%

“…In this decade, there have been many reports that RE(OTf) 3 as a Lewis acid catalyst has been successfully applied to several synthetic reactions. [39][40][41][42][43][44][45] Recently, we have developed RE(OTf) 3 catalyzed Friedel-Crafts reactions [46][47][48][49] and benzyl-etherification, 50) and these reactions proceed smoothly using small amounts of RE(OTf) 3 . During the course of our investigations about Friedel-Crafts acylation, we found that acetyl perchlorate, the mixed anhydride of acetic acid and perchloric acid, which acts as an active acylating agent is generated from acetic anhydride and lithium perchlorate in the presence of RE(OTf) 3 .…”

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confidence: 99%

Scandium(III) Trifluoromethanesulfonate Catalyzed Aromatic Nitration with Inorganic Nitrates and Acetic Anhydride.

Kawada

Takeda

Yamashita

et al. 2002

CHEMICAL & PHARMACEUTICAL BULLETIN

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Nitration of aromatic compounds is one of the most fundamental and useful reactions for introducing the nitrogen atom directly into aromatic rings. [1][2][3][4] This reaction generally requires the use of a potent mixture of concentrated or fuming nitric acid with sulfuric acid, a large amount of acid and its waste after the aqueous work-up procedures often cause serious environmental problems. In order to these issues, there have been some efforts to perform reactions in the absence of sulfric acid. For the solution of this problem, we focused on acyl nitrates, which are known as active nitrating agent. [27][28][29][30][31][32][33][34][35][36] Acyl nitrates are generally produced in situ by the reaction of an excess of concentrated or fuming nitric acid and carboxylic anhydride, or the reaction of silver nitrate and acid chloride. Another method for the generation of acyl nitrates is the reaction of inorganic nitrates and carboxylic anhydride, whereas, in most cases, the nitration by this method is limited to activated substrates. 37) Crivello reported that the acyl nitrates generated from the mixture of ammonium nitrate and trifluoroacetic anhydride and aromatic nitration smoothly proceeded, however, the reaction of ammonium nitrate with acetic anhydride did not produce nitration products. 38) It is known that rare earth metal(III) trifluoromethanesulfonates (rare earth metal(III) triflates, RE(OTf) 3 ) have a high Lewis acidity compared to the corresponding rare earth metal(III) halides, and are stable in water. In this decade, there have been many reports that RE(OTf) 3 as a Lewis acid catalyst has been successfully applied to several synthetic reactions.39-45) Recently, we have developed RE(OTf) 3 catalyzed Friedel-Crafts reactions [46][47][48][49] and benzyl-etherification, 50) and these reactions proceed smoothly using small amounts of RE(OTf) 3 . During the course of our investigations about Friedel-Crafts acylation, we found that acetyl perchlorate, the mixed anhydride of acetic acid and perchloric acid, which acts as an active acylating agent is generated from acetic anhydride and lithium perchlorate in the presence of RE(OTf) 3 . [46][47][48][49] Based on this consideration, the efficient generation of acyl nitrate is expected between an inorganic nitrate and carboxylic anhydride in the presence of RE(OTf) 3 , and we tried to examine the nitration of aromatic compounds using the RE(OTf) 3 -carboxylic anhydride-inorganic nitrate system. Results and DiscussionIn the first place, the catalytic activity of Lewis acids was examined for the nitration of m-xylene using the acetic anhydride-lithium nitrate system. These results are summarized in Table 1. The nitration of m-xylene was carried out in a solution containing 0.3 molar equivalent of Lewis acid, 5.0 molar equivalent of acetic anhydride, and 1.0 molar equivalent of lithium nitrate (LiNO 3 ) at room temperature. 1,3-Dimethyl-2-nitrobenzene (1) and 1,3-dimethyl-4-nitrobenzene (2) as nitration products were obtained. No di-nitrated products were observ...

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Lanthanide trifluoromethanesulfonates as reusable catalysts: catalytic Friedel-Crafts acylation

Abstract: The Friedel-Crafts acylation of substituted benzenes proceeds smoothly by using a catalytic amount of a lanthanide trifluoromethanesulfonate [Ln(OTf),], which is easily recovered from the reaction mixture and reused without a decrease in catalytic activity.

Cited by 129 publications

References 7 publications

Scandium Triflate in Organic Synthesis

Scandium Triflate in Organic Synthesis

Lanthanides and Actinides in Ionic Liquids

Scandium(III) Trifluoromethanesulfonate Catalyzed Aromatic Nitration with Inorganic Nitrates and Acetic Anhydride.

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