Chlorite esters

Chlorite esters, like chlorite salts, are explosively unstable. 

Chlorite esters, like chlorite salts, are explosively unstable. See Silver chlorite, Alone, or lodoalkanes... 

Oxidation of the tetrahydroindolizine 338 with sodium chlorite gives the lactam 339, which rapidly lactonizes to give the pyranoindolizine 340 (Equation 122) <2001T8647>, and the one-pot , three-component reaction between the keto ester 235, acrolein, and o-aminophenol (formally analogous to that of Equation 63) gives the benzoxazolo-naphthyridine 341 (Equation 123) <20010L2145>. 

For the synthesis of amino acids, the reaction of an a-haloalkyl boronic ester 4 with sodium azide and a phase-transfer catalyst in dichloromethane/water requires a large excess of azide in order to form the a-azidoalkyl boronic ester 5 with only 1-2% epimer34. With the exception of R1 = benzyl, where epimerization of 4 is relatively rapid, bromoalkyl boronic esters are preferred. Chloroalkyl boronic esters react so slowly that the azide and dichloromethane may generate hazardously explosive diazidomethane65,66. Chain extension of 5 to 6 proceeds normally. Sodium chlorite, which is known to oxidize aldehydes to carboxylic acids67-69, also oxidizes a-chloroalkyl boronic esters to carboxylic acids34. The azido acid is hydrogenated to the amino acid. 

The reactivity of acidified chlorite solutions is reduced for bleaching some textiles by adding compounds like polyamines, pyrophosphates, and hydrogen peroxide that suppress the formation of chlorine dioxide (57). Another method is to buffer the solution at pH 5—6 to reduce the rate of chlorine dioxide formation. Hydrolysis of anhydrides and esters or oxidation of alcohols can be used to slowly generate acids to promote chlorine dioxide formation (58). Aldehydes also promote chlorine dioxide generation from neutral chlorite solutions, but the effect is greater than simply lowering the pH as they... 

N-Methylated y-amino-p-hydroxy acids are accessible by the usual synthetic sequences, i.e. aldol condensation or y-amino-P-oxo ester reduction, starting from the corresponding N-methylated a-amino acids, but are obtained with low diastereoselectivity. 61-63 Alternatively, Brown allylboration of the ALBoc-ALMe amino aldehyde 16 (R1 = Bzl, X=Boc, Y = Me) gives the allyhc N-methylated intermediate 27 in 64% yield and 90% de (Scheme 12). 64 Oxidative cleavage of the alkenol is performed using the two-step ozonolysis and sodium chlorite oxidation sequence. 

Protection of 194 as a p-methoxybenzylether and subsequent epoxydation led to the trans-epoxide 195, which was transformed into the unsaturated aldehyde 196 by a three-reaction sequence, including regioselective oxirane opening with a 1,3-dithiane anion, hydrolysis of the dithioacetal formed, and dehydration. Chlorite promoted aldehyde oxidation, methyl ester formation, and removal of the hydroxyl protections delivered methyl (+)-shikimate 197 in a remarkable 12% yield from 193. 

Hydrolysis of the 1,3-oxathiane moiety has been accomplished under mild conditions (0°C, 5 min) by the use of N-Chlorosuccinimide-Silver(l) Nitrate. This oxidative hydrolysis produces a-hydroxy aldehydes in good yields and, in addition, two diastereomeric sultines (19) (eq 8). The use of Iodine-for the oxidative hydrolysis of 1,3-oxathianes has also recently been reported. The tertiary a-hydroxy aldehydes are easily oxidized directly to the acids (Sodium Chlorite) or methyl esters (MeOH, I2, KOH) or are conveniently reduced to the diols by direct reduction of the hydrolysis mixture with Sodium Borohydride. The secondary a-hydroxy aldehydes could likewise be reduced to the glycols without racemization however, oxidation required pro-... 

In the final stages of the total synthesis of ustiloxin D, M.M. Joullie and co-workers had to install the amide side-chain onto the already assembled macrocycle.To achieve this goal, the macrocyclic primary alcohol was treated with the Dess-Martin periodinane to generate the corresponding aldehyde, which was subsequently treated with sodium chlorite to afford the carboxylic acid. The carboxylic acid was then coupled with the benzyl ester of glycine to complete the installation of the side-chain in 66% yield for three steps. 

DIMETHYL ESTER of SULFURIC ACID (77-78-1) Combustible liquid (flash point 182°F/83°C). Violent reaction with strong oxidizers, strong acids, strong alkalis, ammonia, ammonium hydroxide, barium chlorite, sodium azide. Incompatible with strong ammonia solutions. Attacks some plastics, rubber, and coatings. 

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