In both catalytic processes, the potassium catalyst 3 exhibited high tolerance towards a number of functional groups. Efficient solid catalyst systems for cyanosilylation of. Feb 27, 2007 the general procedure for the addition of tmscn to carbonyl compounds under nucleophilic catalysis is as follows. Various trimethylsilylated cyanohydrins were isolated in very good to excellent yields. Which compound can be made from an aldehyde and ch3co2ch3.
Organic synthesis document of addition of cyanide group to carbonyl compounds. Solventfree cyanosilylation of carbonyl compounds catalyzed. Hydroboration, cyanosilylation, and sequential cyanosilylation and. Chart 1 aluminium catalysts for the cyanosilylation of carbonyl compounds.
This methodology offers a convenient access to a variety of valuable chiral building blocks, as well as biologically active compounds, such as. Cyanosilylation of aldehydes catalyzed by agi mdpi. A new silicabased scandiumiii interphase catalyst 2 efficiently catalyzes the cyanosilylation of a variety of aldehydes and ketones. An expeditious synthesis of cyanohydrin trimethylsilyl. Cyanosilylation of aldehydes and aliphatic ketones can be carried out in dimethylformamide even without the use of any catalyst. Additionally, cyanosilylation of carbonyl compounds was explored with trimethylsilyl cyanide and aldehydesketones, using the alkali metal precatalyst 3 under mild conditions. Cyanosilylation of carbonyl compounds catalyzed by sodiuml.
Catalyzed cyanosilylation of carbonyl compounds with cyanotrimethylsilane. The catalytic hydrosilylation of ketones is a valuable transformation because it generates protected cyanosilylation reaction of carbonyl compounds is an efficient procedure for the synthesis of silylated cyanohydrins, which are readily converted. The sp2 hybridization of the carbonyl compound means that attack of the nucleophile on the carbonyl carbon may occur from either face. Alkyl groups are electron donating, and so ketones have their effective partial positive charge reduced more than aldehydes two. Typical procedure for hydroborylation of carbonyl compounds. Asymmetric cyanohydrin synthesis from aldehydes and ketones using chiral metal salen complex as catalyst sung soo kim department of chemistry, inha university, incheon 402751, south korea abstract. Geeta devi yadav department of chemistry, university of delhi, delhi, 17 india. A highly efficient organocatalyst for the cyanosilylation of carbonyl compounds under solvent free condition dr. Sample preparation is needed in this work, the possibility of using a photoionization detector pid for analysis of aldehydes and ketones in alcoholic matrices after. In these compounds the carbonyl group is conjugated with an alkene hence the adjective unsaturated, from which they derive special properties. In both catalytic processes, the potassium catalyst 3 exhibited high tolerance towards. Apr 28, 2009 carbonyl compounds undergo reaction with nucleophiles because of the polarization of the co bond. Other aldehydes of industrial significance are mainly used as solvents, perfumes, and flavouring agents or as intermediates in the manufacture of plastics, dyes, and pharmaceuticals. Nheterocyclic carbenes were found to be highly effective organocatalysts in activating tmscn for facile cyanosilylation of carbonyl compounds.
We have developed an efficient catalytic cyanosilylation of carbonyl compounds with an in situ generated alkenephosphine adduct, which is tuned not to couple with a. Cyano transfer from tmscn to aldehydes and ketones proceeds at room temperature in the presence of only 0. A compound containing a carbonyl group is often referred to as a carbonyl compound. Synthesis, characterization and catalytic property of chiral. Carbonyl compounds organic building blocks sigmaaldrich. We report carbonylstabilized phosphorus ylides as general and efficient catalysts for the cyanosilylation of ketones. It is present in carbon dioxide and in methanal, which represent respectively the high and low extremes in the level of oxidation of a carbonyl. The hydrosilylation and cyanosilylation of ketones. An informationefficient mononuclear maingroup catalyst for the cyanosilylation of carbonyl compounds mahendra kumar sharma,a soumen sinhababu,a goutam mukherjee,a gopalan rajaramanb and selvarajan nagendrana adepartment of chemistry, indian institute of technology delhi, hauz khas, new delhi 110 016, india. Activation of tmscn by nheterocyclic carbenes for facile.
The catalytic asymmetric cyanation of carbonyl compounds for example, aldehydes and ketones is an attractive protocol to obtain chiral cyanohydrin derivatives 21. The hydroboration of aldehydes and ketones proceeded efficiently at room temperature to yield, after work up, 1 and 2 alcohols. Solventfree cyanosilylation of carbonyl compounds catalyzed by nbcl 5 bull. Organocatalytic cyanosilylation of carbonyl compounds by. Organophosphorous compounds have also been employed. Nheterocyclic carbenes were found to be highly effective organocatalysts in activating tmscn for facile and mild cyanosilylation of carbonyl compounds. Aluminum monohydride catalyzed selective hydroboration of. Efficient, rapid and solventfree cyanosilylation of aldehydes and. The two unshared electorn pairs of oxygen occupy two of these aos, and the third is involved in sigma bond formation to the carbonyl carbon. A simple and convenient method for the addition of tmscn to carbonyl compounds is described.
Experimental section, general procedure for the cyanosilylation, nmr data of cyanosilylated products, and details of xray structural analysis. Hydroboylation of carbonyl compounds were carried out using the following standard protocol. Hydroboration, cyanosilylation, and sequential cyanosilylation and hydroboration of carbonyl compounds in the presence of a ti iv amido complex as an efficient catalyst adimulam harinath, jayeeta bhattcharjee, koteswar rao gorantla, bhabani s. Catalytic hydroboration and cyanosilylation of a wide range of aldehydes and ketones, with pinacolborane 4,4,5,5 tetramethyl1,3,2dioxaborolane. The general procedure for the addition of tmscn to carbonyl compounds under nucleophilic catalysis is as follows. Apr 16, 2018 the catalytic hydroboration and cyanosilylation processes are high. The carbonyl group is polar because oxygen is more electronegative than carbon this means the strongest intermolecular force between two carbonyl group compounds is dipoledipole however, they can hydrogen bond with compounds like alcohol or water this makes them soluble in water longer chained carbonyl compounds are less soluble as the longer chain gets in the way of the. Cyanosilylation of carbonyl compounds with trimethylsilyl.
A highly efficient and recyclable silicabased scandium. Efficient solid catalyst systems for cyanosilylation of carbonyl compounds with cyanotrimethylsilane onaka makoto 1, higuchi katsumi 1, sugita keisuke 1, izumi yusuke 1. The n,ndiethylacetamide derived phosphorane is identified as an extremely efficient catalyst for the cyanosilylation of dialkyl ketones, alkyl aryl ketones, diaryl ketones, and. The cyanosilylation of carbonyl compounds to form new cc bonds and to protect alcohol functions is an important reaction as the oprotected cyanohydrins can be transformed into a wide range of important intermediates such as. Among them, the cyanosilylation of carbonyl compounds using trimethylsilyl cyanide tmscn is widely utilized for the synthesis of cyanohydrins. Cyanosilylation of carbonyl compounds with trimethylsilyl cyanide catalyzed by an yttrium. Catalyst for the cyanosilylation of carbonyl compounds. Direct chromatographic analysis doesnt allow the determination of carbonyl compounds on this level of concentration.
Aldehyde other carbonyl compounds of industrial use. The catalytic hydrosilylation of ketones is a valuable transformation because it generates protected cyanosilylation reaction of carbonyl compounds is an efficient procedure for the synthesis of. We begin our study of carbonyl compounds with the study of aldehydes and ketones the aldehydeketone oxidation level. It is present in carbon dioxide and in methanal, which represent respectively the high and low extremes in the level of oxidation of a carbonyl carbon. Cyanohydrins can be made from carbonyl compounds by generating cn ions from hcn in the presence of a weak base. In organic chemistry, a carbonyl group is a functional group composed of a carbon atom doublebonded to an oxygen atom.
Cyanosilylation of carbonyl compounds with trimethylsilyl cyanide. Titanium catalyst 1 exhibits high tolerance toward several functional groups. Although the catalyst is chiral, the enantioselectivities observed are generally poor except for one case. Thioureacatalyzed enantioselective cyanosilylation of ketones. The catalytic hydroboration and cyanosilylation processes are high. With respect to cyanosilylation of carbonyl compounds, lalhotf b is the best mononuclear maingroup catalyst known to date, and the catalyzed reaction takes 15 h to complete with 0. Iron catalyzed hydroboration of aldehydes and ketones the. Both the carbon and oxygen atoms are hybridized sp 2, so the system is planar the three oxygen sp 2 aos are involved as follows. Lewis acid catalysis stands as the traditional and proven strategy for activation of carbonyl compounds toward enantioselective reactions.
Hydroboration, cyanosilylation, and sequential cyanosilylation and hydroboration of carbonyl compounds in the presence of a ti iv amido complex as an efficient catalyst. The hydrosilylation and cyanosilylation of ketones catalyzed. Among these are benzaldehyde, which provides the odour and flavour of. Removal of solvent under reduced pressure from the filtrate gave a yellow solid.
Cyanosilylation of carbonyl compounds catalyzed by. On react of the carbonyl group \ t he carbonyl group, co is a structural feature of many different types of compounds. Combined use of an alkene and a phosphine as a nucleophilic. Determination of carbonyl compounds is not so easy. Plumet 9,10 and tian 11 independently reported that phosphonium saltscatalyzed cyanosilylation with aldehydes and ketones. Supported ionic liquidlike phases as organocatalysts for. Asymmetric counteraniondirected lewis acid organocatalysis. Mukaiyama reported that bu3p and ph3p act as catalysts for the cyanosilylation with aldehydes 8. Organocatalytic cyanosilylation of carbonyl compounds has received great attentions in the past few years. Carbonylstabilized phosphorus ylide as an organocatalyst. Solid acid and basecatalyzed cyanosilylation of carbonyl.
Potassium laspartate has been used as a catalyst for the cyanosilylation of carbonyl compounds producing corresponding cyanohydrin trimethylsilyl ethers in excellent yield of up to 98%. However, the nucleophilic center varies from oxygen and sulfur in the catalytic systems such as k 2 co 3, inorganic and organic phosphate salts especially tetrabutylammonium dimethylphosphate, noxides, alkali metal salts of amino acids, or imidazoliumcarbodithioate zwitterions to. The autocatalytic pathway can be initiated by either a neutral ax or an ionic by species. We used the example of hydration formation of gemdiols to illustrate nucleophilic addition to carbonyl compounds. It is common to several classes of organic compounds, as part of many larger functional groups. Alkyl groups are electron donating, and so ketones have their effective partial positive charge reduced more than aldehydes two alkyl substituents vs. It also could be recovered and reused for at least 10 reaction cycles without considerable loss of reactivity. Compounds containing the carbonyl group chubby revision. Pdf a simple and convenient method for the addition of tmscn to carbonyl compounds is described. The magnesiumi complex xylnacnacmg2 was employed as a highly efficient catalyst for the cyanosilylation of a variety of ketones with. Synthesis, characterization and catalytic property of. Browse sigmaaldrich s carbonyl compounds to find products in acid halides, aldehydes, amides, carbonates, carboxylic acid anhydrides, carboxylic acid salts. A highly efficient and recyclable silicabased scandiumiii.
Supported ionic liquidlike phases sillps are able to efficiently catalyse the cyanosilylation of carbonyl compounds using trimethylsilyl cyanide under solventfree conditions. Effect of carbonatesphosphates as nucleophilic catalysts in. Carbonyl compounds undergo reaction with nucleophiles because of the polarization of the co bond. Cyanide addition to carbonyl compounds free download as powerpoint presentation. Pdf solventfree cyanosilylation of carbonyl compounds. Chiral alsalen is used as catalyst for enantioselective cyanosilylation of aldehydes and ketones. Cyanosilylation of carbonyl compounds catalyzed by potassium. Request pdf cyanosilylation of carbonyl compounds catalyzed by sodiumlhistidine an efficient protocol for the addition of trimethyl silanecarbonitrile to carbonyl compounds by employing 1 mol. Aldehydes and ketones carbonyl compounds the carbonyl double bond. The hydrosilylation reaction of carbonyl compounds has emerged as a powerful method in organic synthesis. The catalyst shows high thermal stability up to 300 c and also is stable in both organic and polar solvents. A new attempt was investigated to utilize inorganic solid acids and bases for the promotion of the reaction of cyanotrimethylsilane me 3 sicn with carbonyl compounds. Cyanosilylation of aldehydes catalyzed by agi and cuiiarylhydrazone coordination polymers in conventional and in ionic liquid media. Potassium exchanged zirconium hydrogen phosphate as heterogeneous catalyst in cyanosilylation of carbonyl compounds.
Cyanosilylation of carbonyl compounds catalyzed by potassium l. In the case of initiation by neutral species, dmf or the substrate itself can activate tmscn by coordinating to silicon. The excited carbonyl compounds have radical characters at both carbon and oxygen atoms of the carbonyl group, and hence most of their photoreactions proceed through radical intermediates. Iron catalyzed hydroboration of aldehydes and ketones. Nhccatalyzed cyanosilylation of carbonyl compounds. Cyanide addition to carbonyl compounds cyanide aldehyde. Yuji kikukawa department of applied chemistry, school of engineering, the university of tokyo, 7. Certain aldehydes occur naturally in flavouring agents. Efficient solid catalyst systems for cyanosilylation of carbonyl compounds with cyanotrimethylsilane onaka makoto 1, higuchi katsumi 1, sugita keisuke 1, izumi yusuke 1 1 department of synthetic chemistry, faculty of engineering, nagoya university. Asymmetric cyanohydrin synthesis from aldehydes and.
Effect of carbonatesphosphates as nucleophilic catalysts. We have developed an efficient catalytic cyanosilylation of carbonyl compounds with an in situ generated alkenephosphine adduct. Pdf potassium exchanged zirconium hydrogen phosphate as. The reaction mixture was filtered using a g4 frit containing celite. Carbonyl compounds are molecules containing the carbonyl group, co.
Aldehyde aldehyde other carbonyl compounds of industrial use. Cyanohydrin synthesis by cyanation or cyanosilylation. Asymmetric cyanation with the chiral ruli combined. We report an operationally convenient room temperature hydroboration of aldehydes and ketones employing feacac3 as precatalyst. For this reason, the photoreactions of saturated ketones occur in the uv region, 270290 nm, and of unsaturated ketones in the uv region, 310330 nm. In a similar reaction, ch2co2ch3 ions are generated from ch3co2ch3 by strong bases. The catalytic hydrosilylation of ketones is a valuable transformation because it generates protected cyanosilylation reaction of carbonyl compounds is an efficient procedure for the synthesis of silylated cyanohydrins, which are readily converted into useful. The catalytic potential of carbon nucleophiles has seldom been disclosed due to their reactivity toward carbon electrophiles to form stable carboncarbon bonds, which are too strong to be cleaved for the expected catalytic cycles. Lowvalent magnesium i catalyzed cyanosilylation of ketones. However, the nucleophilic center varies from oxygen and sulfur in the catalytic systems such as k 2 co 3, inorganic and organic phosphate salts especially tetrabutylammonium dimethylphosphate, noxides, alkali metal salts of amino acids, or imidazoliumcarbodithioate. These organic catalysts were efficient for various carbonyl compounds including aromatic, aliphatic and. Catalyst for the cyanosilylation of carbonyl compounds mahendra kumar sharma,a soumen sinhababu,a goutam mukherjee,a gopalan rajaramanb and selvarajan nagendrana adepartment of chemistry, indian institute of technology delhi, hauz khas, new delhi 110 016, india. Nbcl5 is found to possess a strong lewis acid property to transform carbonyl compounds smoothly to the corresponding cyanosilylether in high yields up to 99 % in solvent free conditions. Supported ionic liquidlike phases as organocatalysts for the.
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