V. I. Kornilov

A new method of synthesis of indolyl glycoses

Abstract The copper-catalysed decomposition of acetylated 1-deoxy-1-diazoketoses in the presence of indole affords acetates of higher 1-deoxy-1-(indol-3-yl)ketoses. The constitution of the products was indicated by elemental analysis, infrared and ultraviolet spectroscopy, destructive oxidation, and periodate oxidation. Deacetylation of the acetates with sodium methoxide gave the 1-deoxy-1-(indol-3-yl)ketoses, whereas, on deacetylation by ammonia, 1-deoxy-1-(indol-3-yl)ketosylamines were formed. Periodate-oxidation data indicated that the ketosylamines contain a stable, pyranoid ring.

Synthesis of β-carbolinyl sugars

Abstract Decomposition of penta- O -acetyl-l-deoxy-l-diazo- keto - D - gluco -heptulose, in the presence of N -methylindole and copper powder as catalyst, results in the formation of penta- O -acetyl-l-deoxy-l-( N -methylindol-3-yl)- keto - D - gluco -heptulose ( 1 ). Compound 1 is acylated by carboxylic anhydrides at C-2 of the N -methylindole moiety, and cyclisation of the intermediate diketone, in the presence of 70% perchloric acid, gives indolo-[2,3- c ]-pyrylium perchlorates. With aqueous ammonia, these perchlorates are easily transformed into β-carbolinyl sugars that are close structural analogues of the indole alkaloids harmane, harmine, and melinonine.

Shortest route to 2-deoxyaldonic acids

In the present work we suggest such a procedure that involves 1-C-nitromethylpolyols as potential sources of carbonyl-containing carbohydrate derivatives. Previously we reported a one-pot synthesis of the base nitro derivative III [1]. The universality of this new methods of reductive nitromethylation of aldoses like I and II we confirmed by the synthesis of dicyclohexylidene-D-arabino-hexitol (IV) in a yield of 62%.

Synthesis of ethyl 2,3-anhydro-4,5:6,7-di-O-isopropylidene-D-arabino-heptonate by the Darzens reaction

Ethyl 2,3-anhydro-4,5:6,7-di-O-isopropylidene-D-arabino-heptonate was prepared for the first time by the Darzens reaction from 2,3:4,5-di-O-isopropylidene-D-arabinose and ethyl chloroacetate under the action of metallic sodium in p-xylene. The reaction gives a number of by-products, including ethyl 3-chloro-2-deoxy-3-hydroxy-4,5:6,7-di-O-isopropylidene-D-arabino-heptonate.

Transformation of Acetalized Polyhyroxyketene Thioacetal in Acid-Alcohol Medium

Abstract2,3:4,5-Di-O-cyclohexylidene-L-arabinose diethyl dithioacetal was treated with sodium methylsulfinylmethylide to prepare a novel compound, 4,5-cyclohexylidene-2-deoxy-L-erythro-pent-1-enose diethyl dithioacetal. The product undergoes a series of transformations in anhydrous ethanol in the presence of p-toluenesulfonic acid: alcoholysis of the cyclohexylidene protection, elimination of water, migration of the double bond, formation of an acyclic allyl cation, elimination of the ethylthio group, formation of a cyclic allyl cation, migration of the mercapto group from C1 to C3,addition of alcohol, and formation of an acetalized lactone. The latter was acetalized to obtain a diastereomeric mixture of 5-O-acetyl-2-deoxy-3-S-ethyl-L-threo- and -erythro-pentono-1,4-lactones.

SCISSION OF THE OXIRANE RING OF 5,6‐ANHYDRO‐1,3:2,4‐DI‐O‐ETHYLIDENE‐D‐SORBITOL BY CARBANIONS OF ACETOACETIC AND CYANOACETIC ACID ESTERS

Das D-Sorbit-Derivat (I) reagiert mit Acetessigsaureethylester in Natriummethylat zum kristallinen 7-Lacton (II).