Dirhodium(II) Tetrakis(perfluorobutyrate)-Catalyzed 1,4-Hydrosilylation of .ALPHA.,.BETA.-Unsaturated Carbonyl Compounds

Anada, Masahiro; Tanaka, Masahiko; Suzuki, K.; Nambu, Hisanori; Hashimoto, Shunichi

doi:10.1248/cpb.54.1622

Cited by 20 publications

(7 citation statements)

References 16 publications

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“…The addition reaction of SiH onto the CO bond of octyl acetate is expected to lead to the formation of a SiOCH4, 5, 16, 26–28 bond as shown in Figure 2.…”

Section: Resultsmentioning

confidence: 99%

“…Hydrosilylation reaction of unsaturated molecules have been largely developed with various catalytic systems 1, 2. Particularly, studies on the hydrosilylation reaction of carbonyl groups from ketone and aldehyde are well illustrated in the literature 3–7. It was reported that the yield of the hydrosilylation reactions depends mainly on the catalyst nature such as UV light,8 metal halides, NiCl 2 ,9 ZnCl 2 ,10 and H 2 PtCl 6 11.…”

Section: Introductionmentioning

confidence: 99%

“…1,2 Particularly, studies on the hydrosilylation reaction of carbonyl groups from ketone and aldehyde are well illustrated in the literature. [3][4][5][6][7] It was reported that the yield of the hydrosilylation reactions depends mainly on the catalyst nature such as UV light, 8 metal halides, NiCl 2 , 9 ZnCl 2 , 10 and H 2 PtCl 6 . 11 Transition-metal salts and complexes catalysts were described as very efficient catalysts for the hydrosilylation reaction.…”

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confidence: 99%

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Efficient carbonyl hydrosilylation reaction: Toward EVA copolymer crosslinking

Bonnet

Bounor‐Legaré

Boisson

et al. 2011

J. Polym. Sci. A Polym. Chem.

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In this article, the hydrosilylation reaction of carbonyl groups of acetate derivatives and SiH groups of hydride‐terminated polydimethylsiloxane at high temperature (100–130 °C) are described. Triruthenium dodecacarbonyl, Ru3(CO)12, was used as effective catalyst for hydrosilylation reaction. The hydrosilylation reactions with octyl acetate and 4‐heptyl acetate were investigated by multinuclear NMR spectroscopy (1H, 13C, and 29Si). This work provides evidence of the addition reaction of SiH groups onto carbonyl groups. The influence of the nature of the acetate structure on the reaction kinetics was shown and the slight contribution of side reactions at high temperature highlighted. Hydrosilylation reaction was extent to the crosslinking of ethylene‐vinyl acetate (EVA) copolymer in the same range of temperature. The formation of EVA chemical network was demonstrated by HR‐MAS NMR spectroscopy and by measuring the gel fraction of EVA chains in hot toluene. From Flory theory, the crosslinking density of elastic strand was calculated to be 80 mol m−3 in agreement with the measurements from swelling ratio (VA/SiH molar ratio: 11.8). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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“…The addition reaction of SiH onto the CO bond of octyl acetate is expected to lead to the formation of a SiOCH4, 5, 16, 26–28 bond as shown in Figure 2.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Efficient carbonyl hydrosilylation reaction: Toward EVA copolymer crosslinking

Bonnet

Bounor‐Legaré

Boisson

et al. 2011

J. Polym. Sci. A Polym. Chem.

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“…[2] Exploring rhenium complexes for their use as catalysts, our early work has led to the development of several efficient systems for transfer hydrogenation, dehydrogenative silylation and hydrosilylation. [3] Recently, hydrosilylation reactions using various metals such as zinc, [4 iron, [5] rhodium [6] and copper [7] have been reported, including the work of other authors with rhenium catalysts. [8] Toste et al [8a-c] and Abu-Omar et al [8d-g] proposed new mechanisms for the hy-drosilylation using high oxidation state rhenium oxo complexes as catalysts.…”

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confidence: 99%

“…A variety of ketones were reduced to the corresponding silyl ethers catalyzed by the (Table 3). In most cases the reactions were complete within 2 h or less with excellent yields (entries [1][2][3][4][5][6][7][8]. Substrates containing bulky groups, such as 3, 4-dihydro-1(2H)-naphtha-A C H T U N G T R E N N U N G lenone, 9-fluorenone and 2-decanone, required 3 h for obtaining similar yields (entries 9-11).…”

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confidence: 99%

A Convenient and Efficient Rhenium‐Catalyzed Hydrosilylation of Ketones and Aldehydes

Dong

Berke

2009

Adv Synth Catal

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The easily available rhenium(I) complex [ReA C H T U N G T R E N N U N G (CH 3 CN) 3 Br 2 (NO)] catalyzes the homogeneous hydrosilylation of a great variety of organic carbonyl compounds (ketones and aldehydes). The reaction is quite sensitive to the solvent applied. ChloroA C H T U N G T R E N N U N G benzene was found to be superior over all the other solvents used. Various aliphatic and aromatic silanes were tested. Excellent yields were achieved at 85 8C in chlorobenzene using triethylsilane, the reaction affording TOF values of up to 495 h À1 . A possible reaction mechanism for the hydrosilylation is presented.

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Ligand‐Free Hydrosilylation of Aldehydes Mediated by Highly Active Zinc Metal

Joo

Kim

2018

Bulletin Korean Chem Soc

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The reduction of carbonyl compounds has been generally considered to be a fundamental protocol for the preparation of the corresponding alcohols. Catalytic hydrogenation of carbonyls has long been a traditional method for achieving this. 1 Aside from this protocol, metal-hydride, 2 boron-based reagents, 3 and bio-catalytic reduction 4 are also considered to be suitable methodologies. In addition, an emerging tool is reduction of the carbonyl group in the presence of a transition-metal catalyst. Numerous transition-metals have been extensively examined to successfully complete this transformation, 5 especially in transfer hydrogenation which is a safe and operationally simple protocol utilizing either element hydrogen or metal-hydrides. 5i, j Along with these protocols, a zinc-based reduction process has been extensively applied for reduction of carbonyl compounds, mainly due to the environmental friendliness and economic benefits. Furthermore, the zinc-based reduction protocol could be readily extended to hydrosilylation of carbonyl compounds, thereby providing the corresponding alcohols. Since the first report by Caubere, 6 and pioneering work by Minoun, 7 it has emerged as an attractive synthetic method to reduce carbonyl compounds. 8 When using this approach, zinc complexes such as zinc acetate and diethylzinc, which are particularly activated by nitrogen-chelating ligands, have frequently been used as pre-catalysts. In early studies of zinc-catalyzed hydrosilylation of aldehydes and ketones, both zinc(II) salt and zinc (0) powder worked well to obtain the corresponding alcohols in the presence of metal-hydride and chlorotrimethylsilane. In 2009, Nishiyama et al. reported a successful method for hydrosilylation of carbonyl compounds using zinc acetate as a catalyst without any assistance from ligands. 9 From a synthetic point of view, reactions of carbonyl compounds with zinc metal also have value in novel applicability. A recent study by Len et al. used zinc metal and carbonyl compound for selective reductive pinacol coupling. 10 The reaction was carried out with zinc metal and NH 4 Cl in an aqueous media, yielding the diols as a major product along with small amounts of reduced alcohols. More recently, Dash's group has described a relatively simple process for selective reduction of carbonyls using a combination of zinc metal-powder with an aqueous NH 4 Cl solution as a proton source in THF. The corresponding product alcohols were exclusively produced along with a trace amount of the pinacol product diols (Scheme 1). 11 Inspired by the above results, we were interested in exploring the nature of highly active zinc (Zn*) in the hydrosilylation of carbonyl compounds. To investigate the potential of our strategy, carbonyl compounds were treated with a mixture of highly active zinc and silane in the absence of any other ligands. Herein, we describe the successful development of Zn*-mediated hydrosilylation of aldehydes and ketones, producing the corresponding alcohols as a major product.To elucidate our stra...

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Dirhodium(II) Tetrakis(perfluorobutyrate)-Catalyzed 1,4-Hydrosilylation of .ALPHA.,.BETA.-Unsaturated Carbonyl Compounds

Cited by 20 publications

References 16 publications

Efficient carbonyl hydrosilylation reaction: Toward EVA copolymer crosslinking

Efficient carbonyl hydrosilylation reaction: Toward EVA copolymer crosslinking

A Convenient and Efficient Rhenium‐Catalyzed Hydrosilylation of Ketones and Aldehydes

Ligand‐Free Hydrosilylation of Aldehydes Mediated by Highly Active Zinc Metal

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