Indium(III) Chloride/Chlorotrimethylsilane as a Highly Active Lewis Acid Catalyst System for the Sakurai−Hosomi Reaction

Onishi, Yasunobu; Ito, Takeshi; Yasuda, Makoto; Baba, Akio

doi:10.1002/1099-0690(200205)2002:9<1578::aid-ejoc1578>3.0.co;2-p

Cited by 78 publications

(27 citation statements)

References 38 publications

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“…However, it did not provide any of the desired imine addition product, although this catalyst was very effective for alkyne-aldehyde addition. The failure of the reaction was attributed to the inability of indium(III), although effective in activating aldehyde (52)(53) (Fig. 1, route a), to coordinate and activate the imine effectively in water.…”

Section: Resultsmentioning

confidence: 76%

Cu(I)-catalyzed direct addition and asymmetric addition of terminal alkynes to imines

Wei

Mague²,

Li³

2004

Proc. Natl. Acad. Sci. U.S.A.

198

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A Cu(I)-catalyzed direct addition of alkynes to imines was developed. The process is simple and provides a diverse range of propargylamines in high enantiomeric excess and good yield both in water and in toluene. The absolute configuration of such addition products has been determined by x-ray crystallography.A s in the case for the addition reaction of carbanions to the carbonyl group of aldehydes and ketones (1-4), the addition of organometallic reagents to the CAN bonds of imines or imine derivatives is an important reaction in organic synthesis (5-9). The carbon-carbon bond-forming method, which uses alkynes as a carbon nucleophile source, is a useful method in synthesis (10, 11). The resulting alkynyl amine derivatives can undergo further transformations and are versatile synthetic tools (12)(13)(14). However, the reactive alkynilides are usually prepared from terminal alkyne by using highly reactive organometallic reagents such as BuLi (15,16), EtMgBr (17,18), or LDA (19,20) in a separate step, and many metal alkynilides are not easy to handle because the reaction must be carried out under anhydrous solvent, inert atmosphere, and low temperature conditions. Therefore, the development of a method for the direct alkynylation of imines that does not use a stoichiometric amount of highly reactive organometallic reagent and can be performed under mild conditions would be highly desirable. Additionally, there has been greater interest in recent years in developing environmentally friendly reactions in aqueous media (21,22).Optically active propargyl amines are important synthetic intermediates for the synthesis of various nitrogen compounds and are components of bioactive compounds or natural products (23-25). Recently, great efforts have been made to develop the methodology for generating propargylamines (26-33). Some direct alkynylations of carbonyl compounds with terminal alkynes have been reported (34-37). Miura (38) has reported the addition of acetylene to nitrones in the presence of a catalytic amount of CuI with K 2 CO 3 as the base and phosphine-and nitrogen-containing compounds as the ligands in N,NЈ-dimethylformamide at 80°C under nitrogen, to give a (2 ϩ 2) coupling product along with a redox product, alkynyl imine. Carreira (39-41) has used a Zn(II)-catalyzed process in CH 2 Cl 2 for the addition of terminal alkynes to nitrones to form propargyl N-hydroxyamine adducts and recently reported (42) the addition of terminal alkynes to imines by an iridium catalyst in toluene or under neat conditions. Ishii (43) reported an ''unexpected'' case of the addition of alkyne to imine by an Ir(I) catalyst. Jiang (44) has reported the addition of terminal alkynes to imines by using ZnCl 2 and Et 3 N as catalysts and TMSCl as the Lewis acid for the activation of imines. Methods for the catalytic preparation of optically active propargyl amines are still limited (10-14, 30, 31).One of our ongoing interests is in the development of transition metal-catalyzed carbon-carbon bond formation in water (45-48). We have rec...

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Section: Resultsmentioning

confidence: 76%

Cu(I)-catalyzed direct addition and asymmetric addition of terminal alkynes to imines

Wei

Mague²,

Li³

2004

Proc. Natl. Acad. Sci. U.S.A.

198

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“…A 100 mmolscale reaction of benzaldehyde with allyltrimethylsilane in the presence of the Cu 2þ -mont catalyst afforded 4-phenyl-1-buten-4-ol in 86% yield. In contrast to previously reported homogeneous aluminum bis(trifluoromethylsulfonyl)amides, 107 ytterbium trichlorides, 108 trimethylsilylmethanesulfonates, 109 indium trichloride/chlorotrimethylsilane, 110 and heterogeneous Al-and K-10 montmorillonites, 111 the Cu 2þ -mont catalyst system is non-polluting and recyclable, and eliminates halogenated reagents and solvents.…”

Section: Catalysis Of Scmentioning

confidence: 83%

“…11,12 A stoichiometric hydroxyapatite (HAP), Ca 5 (OH)(PO 4 ) 3 , was synthesized from Ca(NO 3 ) 2Á 4H 2 O and (NH 4 ) 2 HPO 4 by the precipitation method described in the literature. 13 The HAP was stirred in an aqueous solution of RuCl 3Á nH 2 O at room temperature for 24 h. The obtained slurry was filtered, washed with deionized water, and dried overnight at 110 C, yielding RuHAP as a dark brown powder. 4a The X-ray diffraction (XRD) peak positions of the RuHAP were identical to those of the parent HAP.…”

Section: Hydroxyapatitementioning

confidence: 87%

Design of High-Performance Heterogeneous Metal Catalysts for Green and Sustainable Chemistry

Kaneda¹,

Ebitani²,

Mizugaki³

et al. 2006

Bulletin of the Chemical Society of Japan

142

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This account reviews a novel approach to designing high-performance heterogeneous metal catalysts using hydroxyapatites, montmorillonites, and hydrotalcites as macroligands of active metal species for aerobic alcohol oxidations, carbon-carbon bond formations, and one-pot syntheses. The catalytic systems using the above heterogeneous catalysts offer significant benefits in achieving environmentally friendly organic syntheses aiming towards Green and Sustainable Chemistry. Furthermore, the present preparation method for the immobilization of metal species is strikingly simple and allows a strong protocol for creating various nanostructured and functionalized heterogeneous catalysts.Green and Sustainable Chemistry (GSC) is a revolutionary philosophy that aims to bring about a sustainable society by improvement of the safety and environmental aspects of chemical processes and reduction of the risks of chemical products to people and the environment.1 The emphasis is on eliminating waste at the source-primary pollution prevention-rather than finding incremental end-of-pipe solutions. This concept aims to solve the societal problems of the last century associated with the mass production and consumption of materials, and plays a prime role in providing a venous function in society, encouraging reuse and circulation of resources.One of the powerful solutions in the move toward GSC is the replacement of traditional synthetic methods using harmful stoichiometric reagents that produce vast amounts of waste with cleaner and simple catalytic alternatives with high atom efficiency 1a and low E-factors. 1b Catalytic chemistry, therefore, is of ever-increasing importance because catalysis is a key element in material transformations at atomic and molecular levels, which are an essential realm of chemistry and chemical processes.Our approach to GSC is to develop a highly functionalized heterogeneous metal catalyst based on the unique characteristics of natural layered inorganic materials such as hydroxyapatite, montmorillonite, and hydrotalcite, by using them as macroligands for metal species.2 We consider the above inorganic materials to be advanced nano-scaled catalyst supports allowing for the control of the location of catalytically active metal species, which can be found, for example, on the surface, among the layers, or in the interlayer space. Furthermore, these materials are capable of creating catalytically active metal species responsible for targeted organic transformations involving monomers, chain-like species or giant clusters. The creation of well-defined active metal sites on a solid surface, as characterized by X-ray absorption spectroscopy, not only opens up an avenue to materials that boost catalytic performance, but also aids in the understanding of the molecular basis of heterogeneous catalysis. Another advantage of these catalysts is the possibility of a one-pot synthesis based on a cooperative action by several immobilized active species on the solid surface as multifunctional catalysts. The target react...

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“…This idea was based on the previous report of a Hosomi-Sakurai reaction catalyzed by the combined Lewis acid of InCl 3 and Me 3 SiCl. 19 In the present reaction system, the formation of In-Si combined Lewis acid was expected because Me 3 SiCl was generated as noted in Scheme 3. It was anticipated that this combined Lewis acid would accelerate the subsequent addition of the silyl nucleophile to the aldehyde.…”

Section: Three-component Tandem Reactionsmentioning

confidence: 99%

Indium-catalyzed coupling reaction between silyl enolates and alkyl chlorides or alkyl ethers

et al. 2009

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Indium(III) Chloride/Chlorotrimethylsilane as a Highly Active Lewis Acid Catalyst System for the Sakurai−Hosomi Reaction

Cited by 78 publications

References 38 publications

Cu(I)-catalyzed direct addition and asymmetric addition of terminal alkynes to imines

Cu(I)-catalyzed direct addition and asymmetric addition of terminal alkynes to imines

Design of High-Performance Heterogeneous Metal Catalysts for Green and Sustainable Chemistry

Indium-catalyzed coupling reaction between silyl enolates and alkyl chlorides or alkyl ethers

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