2-Trimethylsiloxy- -nitril

The use of the y-(trimethylsiloxy)nitrile derivatives (190) as a route to 1,4-bifunctional units is exemplified in a convenient synthesis of jasmonoid compounds. The addition of the Grignard reagent to the cyano group as the homologation step results in the keto alcohol (191) after subsequent hydration. The y-ketocarboxylic add (192) obtained from the... 

Trimethylsilyl cyanide. 13, 87-88 14,107 15,102-104 17,89 18,381-382 19,375 fi-Trimethylsiloxy nitriles. The TiCl -promoted epoxide opening is subject to asymmetric induction by chiral ligands. The derivatization of aryl ketones is efficiently promoted by LiClO and LiBF. For safety consideration the use of LiBF /MeCN is recommended. 

The masked acrylate anion (70) can be condensed with epoxides leading to a-alkylidene-lactones (71) after a retro-Diels-Alder reaction the generality of this method remains to be seen. Compounds (71) can also be obtained in generally moderate overall yields from enolates of y-trimethylsiloxy-nitriles by... 

Reactions with Oxiranes, Oxetanes, and Aziridines. Lewis acids, lanthanide salts, and titanium tetraisopropoxide or aluminum isopropoxide catalyze the reactions of cyanotri-methylsilane with oxiranes, oxetanes, and aziridines, yielding ring-opened products. The nature of the products and the regio-selectivity of the reaction are primarily dependent on the nature of the Lewis acid, the substitution pattern in the substrate, and the reaction conditions. Monosubstituted oxiranes undergo regiospe-cific cleavage to form 3-(trimethylsiloxy)nitriles when refluxed with a slight excess of cyanotrimethylsilane in the presence of a catalytic amount of potassium cyanide-18-crown-6 complex (eqs 8-10). The addition of cyanide occurs exclusively at the least-substituted carbon. 

Good yields of 3-(trimethylsiloxy)nitriles are also obtained from the reactions of oxiranes with cyanotrimethylsilane in the presence of lanthanide salts, or when the reaction is catalyzed by AICI3 or diethylaluminum chloride (eq 11). Ring opening of chiral glycidyl derivatives by MesSiCN catalyzed by Ti(0-i-Pr)4 or Al(0-i-Pr)3 occurs in a regiospeciflc and highly stereoselective manner (eq 12). ... 

Eine niitzliche, breit anwendbare Variante der in Bd. XI/1, S.571, beschriebenen Reduk-tion von a-Hydroxy-carbonsaure-nitrilen (Cyanhydrinen) als Teil der Umwandlung von Aldehyden Oder Ketonen in Amino-alkohole unter Verlangerung der C-Kette um ein C-Atom (eine CH2-Gruppe) besteht in der Reduktion von a-Trimethylsiloxy-carbonsaure-nitrilen (aus O-Silyl-enolen und Cyanwasserstoff Oder besser aus Aldehyden oder Ketonen und Cyan-trimethyl-silan) mit Lithiumalanat5-7 die a-Siloxy-carbonsaure-nitrile brau-chen dabei nicht in reiner Form isoliert zu werden. 

Moreover, the formation of enoxy-silanes via silylation of ketones127 by means of N-methyl-N-TMS-acetamide (1 72) in presence of sodium trimethylsilanolate (173) was reported in 1969 and since then, the use of silylating reagents in presence of a catalyst has found wide appreciation and growing utilization as shown in recent papers128-132 (Scheme 27). Diacetyl (181) can be converted by trifluoromethylsul-fonic acid-TMS-ester (182) into 2,3-bis(trimethylsiloxy)-l, 3-butadiene (7treatment with ethyl TMS acetate (7 5)/tetrakis(n-butyl)amine fluoride l-trimethylsiloxy-2-methyl-styrene (i<56)130. Cyclohexanone reacts with the combination dimethyl-TMS-amine (18 7)/p-toluenesulfonic acid to 1-trimethylsiloxy-l-cyclohexene (iSS)131. Similarly, acetylacetone plus phenyl-triethylsilyl-sulfide (189) afford 2-triethylsiloxy-2-pentene-4-one (790)132. ... 

The most systematically investigated acyl anion equivalents have been the IMS ethers of aromatic and heteroaromatic aldehyde cyanohydrins, TBDMS-protected cyanohydrins, - benzoyl-protected cyanohydrins, alkoxycaibonyl-protected cyanohydrins, THP-protected cyanohydrins, ethoxyethyl-protect cyanohydrins, a-(dialkylamino)nitriles, cyanophosphates, diethyl l-(trimethylsiloxy)-phenyimethyl phosphonate and dithioacetals. Deprotonation di these masked acyl anions under the action of strong basie, usually LDA, followed by treatment with a wide varies of electrophiles is of great synthetic value. If the electrophUe is another aldehyde, a-hydroxy ketones or benzoins are formed. More recently, the acyl caibanion equivalents formed by electroreduction of oxazolium salts were found to be useful for the formation of ketones, aldehydes or a-hydroxy ketones (Scheme 4). a-Methoxyvinyl-lithium also can act as an acyl anion equivalent and can be used for the formation of a-hydroxy ketones, a-diketones, ketones, y-diketones and silyl ketones. - - ... 

Isophthaloyl dichloride Isoprene N-Isopropylaniline Isopropyl mercaptan Isostearamidopropyl dimethylamine Isostearyl alcohol Kojic acid Lauryl nitrile d-Limonene Linolenic acid y-Linolenic acid Manganese nitrate 3-Mercaptopropionic acid 3-Mercaptopropylmethyldimethoxysilane Mercaptopropyltrimethoxysilane 3-Methacryloxypropyltris (trimethylsiloxy) silane o-Methoxybenzaldehyde Methoxydiglycol Methoxyethanol Methoxyisopropanol... 

The ambident nature of cyanotrimethylsilane can lead to the formation of nitriles or isocyanides, depending on the nature of the catalyst. For example, cyanotrimethylsilane reactions with epoxides and oxetanes catalyzed by soft Lewis acids give rise to 2-(trimethylsiloxy) isocyanides arising by attack on the more substituted carbon (eqs 15 and 16).Milder reaction conditions and better yields of isocyanides can be realized when the reaction of cyanotrimethylsilane with oxiranes is carried out in the presence of Pd(CN)2, SnCL, or MesGa (eq 17). Isocyanides are useful precursors for the synthesis of /3-amino alcohols and oxazolines. 

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