Ketones silanes

Tetrabutylammonium fluoride, 286 Silanes (see also Allylic compounds, a, 13-Epoxy silanes, Ketones, Silyl enol ethers, Vinylsilanes)... 

Ligand Rh- Cat. L/Rh S/C Silane Silane/ Ketone Solvent TcmpTTimc (°C/h) Product 1 -phenylethanol (4) ... 

Ketone Silane Ketone/Rh Time (hr) Product insolubilized catalyst (%ee)6 Product soluble catalyst (%ee)b... 

Catalyst Ti- Silane Ketone Solvent L/Ti Ketone/Ti Silane/ Temp/Time Product secondary alcohol Ref. 

Silane Ketone Ligand in 5 or 6 Optical yield (%) (configuration) Reference... 

The concept of silyl enol ether synthesis via / -elimination from a Brook rearrangement-derived carbanion also appeared in Wicha s studies on additions of 1-phenyl-l//-tetrazol-5-yl (PT) sulfonyl anions to acyl silanes. When PT sulfone 34 was deprotonated in the presence of acyl(triphenyl)silane, ketone 36 was isolated in good yield after hydrolysis of the silyl enol ether intermediate 35. The mechanism involved addition of the... 

In this chapter, the scope, mechanism, and recent progress of zirconocene (Il)-mediated cyclization reactions are introduced. Zirconocene(II) is a very important reagent for organometallic chemistry, synthetic chemistry, and polymer chemistry. Zirconocene(II) is capable of coordinating with unsaturated compounds. Further reactions could lead to zirconocene(IV) species, zirconacycles, C-C bond formation, C-X bond formation, and synthesis of carbocycles and heterocycles. Zirconocene(lI)-mediated cyclization of bis(alkynyl)silane gives zirconacyclobu-tene-silacyclobutene complexes, which could react with alkyne, bis(alkynyl)silane, ketone, nitrile, and isocyanate and could be applied in the synthesis of various valuable products. 

No. Ketone Silane Ketone/ Rh" Time, hr Isolated alcohol chemical yield, % Optical yield,% Optical yield, % with the soluble Rh-(+)-diop catalyst ... 

Results corresponding to experiments where silane/ketone = 2. 

Ketone Silane S/C Silane/Ketone Solvent Yield (%) % ee abs config Ref. 

A McMurry coupling of (176, X = O Y = /5H) provides ( )-9,ll-dehydroesterone methyl ether [1670-49-1] (177) in 56% yield. 9,11-Dehydroestrone methyl ether (177) can be converted to estrone methyl ether by stereoselective reduction of the C —double bond with triethyi silane in triduoroacetic acid. In turn, estrone methyl ether can be converted to estradiol methyl ether by sodium borohydride reduction of the C17 ketone (199,200). 

Tl mediated Inter or intramolecular addition of allytic silanes to ouMnsaiurated ketones or to aldehydes. 

Nevertheless Kipping made a number of contributions of value to the modem silicone industry. In 1904 he introduced the use of Grignard reagents for the preparation of chlorosilanes and later discovered the principle of the inter-molecular condensation of the silane diols, the basis of current polymerisation practice. The term silicone was also given by Kipping to the hydrolysis products of the disubstituted silicon chlorides because he at one time considered them as being analogous to the ketones. 

In a cross-coupling benzoin condensation of two different aldehydes, usually a mixture of products is obtained, with the ratio being determined by the relative stabilities of the four possible coupling products under thermodynamic control. If, however, an acyl silane, e.g. 5, is used as the donor component, the a-silyloxy-ketone 6 is obtained as a single product " ... 

Of particular interest are reactions between a-hydroxy ketones and allyl(trifluoro)silanes which proceed with participation of the hydroxy group via a pentacoordinated allylsilane, with intramolecular delivery of the allyl group to the ketone. Excellent stereoselectivity is obtained at up to three contiguous stereogenic centers66. 

Very few optically active cyanohydrins, derived from ketones, are described in the literature. High diastcrcosclectivity is observed for the substrate-controlled addition of hydrocyanic acid to 17-oxosteroids27 and for the addition of trimethyl(2-propenyl)silane to optically active acyl cyanides28. The enantioselective hydrolysis of racemic ketone cyanohydrin esters with yeast cells of Pichia miso occurs with only moderate chemical yields20. 

A novel and versatile method for preparing polymer-supported reactive dienes was recently developed by Smith [26]. PS-DES (polystyrene diethyl-silane) resin 28 treated with trifluoromethanesulfonic acid was converted to a polymer-supported silyl triflate 29 and then functionalized with enolizable a,jS-unsaturated aldehydes and ketones to form silyloxydienes 30 and 31 (Scheme 4.4). These reactive dienes were then trapped with dienophiles and the Diels Alder adducts were electrophilically cleaved with a solution of TFA. 

Silanes And Base. In the presence of bases, certain silanes can selectively reduce carbonyls. Epoxy-ketones are reduced to epoxy-alcohols, for example with (MeO)3SiH and LiOMe. ° Controlling temperature and solvent leads to different ratios of syn- and anti- products.Silanes reduce ketones in the presence of BF3-OEt2 ° and transition metal compounds catalyze this reduction. ... 

It has been known since 1954 that aldehydes or ketones are reduced by silanes to give silylated primary or secondary alcohols [41]. Reduction of ahphatic aide-... 

Highly enantioselective hydrosilylation of aliphatic and aromatic carbonyl compounds such as acetophenone, methyl phenethyl ketone 1813, or deuterobenz-aldehyde 1815 can be readily achieved with stericaUy hindered silanes such as o-tolyl2SiH2 or phenyl mesityl silane 1810 in the presence of the rhodium-ferrocene catalyst 1811 to give alcohols such as 1812, 1814, and 1816 in high chemical and optical yield [47] (Scheme 12.14). More recently, hydrosilylations of aldehydes... 

The hydrosi(ly)lations of alkenes and alkynes are very important catalytic processes for the synthesis of alkyl- and alkenyl-silanes, respectively, which can be further transformed into aldehydes, ketones or alcohols by estabhshed stoichiometric organic transformations, or used as nucleophiles in cross-coupling reactions. Hydrosilylation is also used for the derivatisation of Si containing polymers. The drawbacks of the most widespread hydrosilylation catalysts [the Speier s system, H PtCl/PrOH, and Karstedt s complex [Pt2(divinyl-disiloxane)3] include the formation of side-products, in addition to the desired anh-Markovnikov Si-H addition product. In the hydrosilylation of alkynes, formation of di-silanes (by competing further reaction of the product alkenyl-silane) and of geometrical isomers (a-isomer from the Markovnikov addition and Z-p and -P from the anh-Markovnikov addition. Scheme 2.6) are also possible. 

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