Isonitrile 2-amino alcohol

Lithiated isonitriles have been treated with oxirans to give 3-hydroxyalkyl isonitriles (305) these have been hydrolysed to 3-amino alcohols, and cyclized to oxazines (306). From oxetane, 4-hydroxyalkyl isonitriles were obtained and these were cyclized to oxazepines in low yield (Scheme 142). ... 

Silyl cyanides react enantioselectively with such electrophiles as aldehydes, ketones, imines, activated azines, or,/ unsaturated carbonyl compounds, epoxides, and aziridines in the presence of chiral Lewis acid catalysts to give functionalized nitriles, versatile synthetic intermediates for hydroxy carboxylic acids, amino acids, and amino alcohols (Tables 3-6, 3-7, 3-8, and 3-9, Figures 3-6, 3-7, and 3-8, and Scheme 3-154). ° Soft Lewis acid catalytst, the reaction of epoxides with trimethylsilyl cyanide often leads to isonitriles, which are derived from silylisonitrile spiecies (Schemes 3-155 and 3-156). Soft Lewis base such as phosphine oxide also catalyzes the reaction and cyanohydrin silyl ethers of high ee s are isolated. 

The following compounds are unaffected by bis(p-methoxyphenyl) telluroxide dithi-olanes, enamines, aldehydes, ketones, alcohols, pyrroles, indoles, amino acids, aromatic amines, monohydroxyarenes, esters, hindered thiocarbonates, isonitriles, oximes, arylhy-drazones, sulphides, and selenides. ... 

The compound reacts with alcohols, phenols and amines to form products similar to those obtained from the corresponding reaction with COCI [1358]. Depending upon the conditions and stoicheiometry, carbonates and chloroformates [612,1380], carbamates [1380], isocyanates [1184] and ureas [938] can be obtained with diphosgene, in addition to more complicated products such as carbamoyl chlorides, imidic chlorides, carboxylic acid chlorides, isonitriles and IV-carboxy-Q-amino acid anhydrides [1358]. 

Polymer-bound isonitrile (423), obtained from TentaGel-NH2 through treatment of the resin with formic acid and acetic anhydride, followed by dehydration of the resulting formamide with tosyl chloride and pyridine, has been employed in the preparation of N-substituted amino add ester [349]. Thus, Ugi MCR, performed in the presence of an alcohol instead of the carboxylic component, gave rise to an imino-ether spedes (426). Several Lewis acids were tested in searching for optimal reaction conditions. Boron trifluoride etherate displayed the better yields in term of desired product of the Ugi-type reaction. Amino acid methyl esters (427) were thus obtained when using methanol as the alcohol component, after deavage from the resin of the intermediate imino-ethers by an acetone/water mixture (Scheme 87). 

The Ugi reaction is the synthesis of an a-amino acid amide by reaction of an aldehyde with an amine and an isonitrile in the presence of zinc chloride and formic acid. )3-D-Galactosylamine has been proposed as a chiral amine partner whose alcohol functions are protected by esterification with pivalate groups (reaction 8.7) (Kunz and Pfrengle 1988). The reaction is carried out in oxolane between -75 and -25°C. The diastereomeric mixture obtained corresponds to a d/l ratio close to 95 5. The pure D-isomer is obtained by recrystallization in heptane. It is known that the bond between a sugar molecule and nitrogen is easy to cleave in glycosylamines (see Section 3.6.2). 

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