Sławomir Jarosz

Sucrose chemistry and applications of sucrochemicals.

Publisher Summary This chapter discusses sucrose chemistry and the applications of sucrochemicals. The use of sucrose as a chemical raw material was first motivated by the desire to increase the small proportion of the total production dedicated to the applications of higher value, essentially for nonfood uses. The conformational structure of sucrose is essentially based on the intramolecular hydrogen-bond network that connects hydroxyl groups from the glucose and the fructose moieties. Some scales of relative acidity of the hydroxyl groups of sucrose, converging on the highest acidity for OH-2, can be established either by semi-empirical calculations or be deduced from the distribution of the regio-isomers after selective substitution. It is found that because of the high stability of the ether function, etherification of unprotected sucrose leads to a kinetic distribution of products directly reflecting the relative reactivity of the hydroxyl groups. Specific microorganisms, yeasts, and bacteria can also convert sucrose into other alcohols, as well as organic acids, amino acids, and vitamins. All these biological processes have been improved with the help of modern biotechnology, making them more chemically and economically efficient and to direct them toward new and useful chemical products.

Stereospecific synthesis of 5,6-dihydro-2H-pyran system. High-pressure cycloaddition of 1:2,3:4-di-0-isopropylidene- α-D-galactopyranose-6-ulose to 1-methoxybuta-1,3-diene

Abstract The high-pressure cycloaddition of 1:2,3:4-di-0-isopropylidene- α-D-galactopyranos-6-ulose (3) to 1-methoxybuta-1,3-diene (1) afforded diastereoisomerically pure cycloadduct 4 whose absolute configuration was determined.

Amino-acid templated assembly of sucrose-derived macrocycles.

C(2)-Symmetrical chiral macrocycles containing two sucrose units were prepared by an amino acid templated macrocyclization reaction between appropriate sucrose-based linear precursors and ethylenediamine.

Stereoselective reduction of higher sugar enones with zinc borohydride

Abstract The higher sugar enones * 3- O -benzyl-5-deoxy-5- C -[( E )-7-deoxy-1,2:3,4-di- O -isopropylidene-α- d - galacto -heptopyranos-6-ulos-7-ylidene]-1,2- O - isopropylidene-α- d -xylofuranose ( 2a ), 3- O -benzyl-5-deoxy-1,2- O -isopropylidene-5- C -[methyl ( E )-2,3,4-tri- O -benzyl-7-deoxy-α- d - gluco -heptopyranosid-6-ulos-7-ylidene]-α- d -xylofuranose ( 3a ), and 3- O -benzyl-6- C -[( E )-6- O -benzyl-7-deoxy-1,2:3,4-di- O -isopropylidene- l - glycero -α- d - galacto - heptopyranos-7-ylidene]-6-deoxy-1,2- O -isopropylidene-α- d - xylo -hexofuranos-5-ulose ( 4a ) on reduction with zinc borohydride afforded with high diastereoselectivities (∼95:5) the higher sugar allylic alcohols 3- O -benzyl-5-deoxy-5- C -[( E )-7-deoxy-1,2:3,4-di- O -isopropylidene- d - glycero -α- d - galacto -heptopyranos-7-yliden]-1,2- O -isopropylidene-α- d -xylofuranose ( 2b ), 3- O -benzyl-5-deoxy-1,2- O -isopropylidene-5- C -[methyl ( E )-2,3,4-tri- O -benzyl-7-deoxy- d - glycero -α- d - gluco -heptopyranosid-7-ylidene]-α- d -xylofuranose ( 3b ), and 3- O -benzyl-6- C -[( E )-6- O -benzyl-7-deoxy-1,2:3,4-di- O -isopropylidene- l - glycero -α- d - galacto -heptopyranos-7- ylidene]-6-deoxy-1,2- O -isopropylidene-α- d -glucofuranose ( 4b ). The configurations at the new chiral centres in 2b – 4b were R . The diastereoisomeric S -alcohols ( 2c – 4c ) were obtained from the R isomers by a modified Mitsunobu reaction.

From Sugar Allyltin Derivatives to Chiral Dienoaldehydes and Trienoates1

Abstract Sugar dialdoses 5, 9, 15, and 16 were converted into allyltin derivatives 4, 12, 13, and 14, in yields of 35–47% respectively. Treatment of 4, 12, and 13 with a mild Lewis acid (ZnCl2) in methylene chloride caused rearrangement to appropriate dienoaldehydes 1, 19, and 20 which were converted into trienes 2, 21, and 22, respectively, by reaction with Ph3P═CHCO2Me.

Regio- and Stereoselective Transformations of Sucrose at the Terminal Positions

Chemistry of sucrose emphasizing regio- and stereoselective transformations performed at the terminal positions (C-1′ and/or C-6 and/or C-6′) is reviewed. 2,2′,3,3′,4-Penta-O-benzyl sucrose is proposed as particularly useful substrate for the preparation of modified derivatives such as amines, uronic acids, crown ether analogues with incorporated sucrose backbone, and so-called “higher sucroses”, i.e. compounds elongated at either “end” by up to 9 carbon atoms. Application of benzyl protecting groups makes possible synthesis of free sucrose analogues by simple removing of the protecting groups by hydrogenolysis without affecting the very labile glycosidic bond.

INTRAMOLECULAR DIELS-ALDER REACTION OF CHIRAL, HIGHLY OXYGENATED TRIENOATES DERIVED FROM SUGAR ALLYLTINS

Abstract The Lewis acid catalyzed intramolecular Diels-Alder reaction of sugar derived trienoates 3 led preferably to bicyclic endo-adducts 4 . The best stereoselectivity was observed for cyclization of the L-arabino-trienoate 3b , in which only one isomer (trans) was formed. High pressure (15 kbar) cycloaddition of 3a, 3b , and 3c , led to single stereoisomers 4a, 4b , and 4c in good yields. Conversion of adduct 4a to chiral cyclopentanes was described.

Preparation of higher-carbon sugars by stereoselective osmylation of related allylic alcohols☆

Abstract The catalytic osmylation of the following higher-carbon sugar allylic alcohols and enones was examined. 3- O -Benzyl-5-deoxy-5- C -[( E )-7-deoxy-1,2:3,4-di- O -isopropylidene-α- d - galacto -heptopyranos-6-ulos-7-ylidene]- 1,2- O -isopropylidene-α- d -xylofuranose ( 5 ) afforded 93% of 3- O -benzyl-6- C -(1,2:3,4-di- O -isopropylidene-α- d -galacto- hexopyranos-6-ulos-6-yl)-1,2- O -isopropylidene- l - glycerp -α- d - gluco - ( 10 ) and d - glycero -β- l - ido -hexofuranose ( 11 ) in the ratio 2:3. 3- O -Benzyl-5-deoxy-5- C -[( E )-7-deoxy-1,2:3,4-di- O -isopropylidene- d - glycero -α- d - galacto -heptopyranos-7-ylidene]-1,2 - O -isopropylidene-α- d -xylofuranose ( 6 ) gave 75% of 3- O -benzyl-6- C -(1,2:3,4-di- O -isopropylidene- d - glycero -α- d - galacto -hexopyranos-6-yl)-1,2- O - isopropylidene- l - glycero -α- d - gluco - ( 12 ) and d - glycero -β- l - ido -hexofuranose ( 13 ) in the ratio 4:1. The l - glycero isomer ( 7 ) of 6 afforded 75% of 3- O -benzyl-6- C -(1,2:3,4-di- O -isopropylidene- l - glycero -α- d - galacto -hexopyranos-6-yl)-1,2- O -isopropylidene- l - glycero -α- d - gluco - ( 14 ) and - d - glycero -β- l - ido - hexofuranose ( 15 ) in the ratio 53:47. 3- O -Benzyl-6-deoxy,1,2- O -isopropylidene-6- C -[methyl ( E )-2,3,4-tri- O -benzyl-6-deoxy-α- d -glucopyranosid-6-ylidene]-α- d - xylo -hexofuranos-5-ulose ( 8 ) gave 65% of 3- O -benzyl-1,2- O -isopropylidene-6- C - [methyl2,3,4-tri- O -benzyl- d - glycero -α- d - gluco -hexopyranosid-6-yl]-α- d - gluco - ( 19 ) and -[ l - glycero -α- d - gluco ]-β- l - ido -hexofuranos-5-ulose ( 20 ) in the ratio 55:45. 3- O -Benzyl-6-deoxyl-1,2- O -isopropylidene-6- C -[methyl ( E )-2,3,4-tri- O -benzyl-6-deoxy-α- d -glucopyranosid-6-ylidene]-α- d -glucofuranose ( 9 ) afforded 71% of 3- O -benzyl,1,2- O -isopropylidene-6- C -[methyl 2,3,4-tri- O -benzyl- d - glycero -α- d - gluco - hexopyranosid-6-yl]- d - glycero -α- d - gluco - ( 21 ) and -[ l - glycero -α- d - gluco -]- d - glycero -α- d - gluco -hexofuranose ( 22 ) in the ratio 9:1. The configuration of all new compounds were assigned by X-ray, chemical, and spectral correlations. These reactions followed Kishis rule, except that of 5 which afforded mainly the anti -Kishi product 11 .

CROWN ETHER ANALOGS FROM SUCROSE

A convenient synthesis of 1′,2,3,3′4,4′-hexa-O-benzylsucrose (4) from the free disaccharide is presented. Diol 4 and previously obtained 1′-O-benzyloxymethyl-2,3,3′,4,4′-penta-O-benzylsucrose (3) served as precursors for chiral crown ether analogs containing a sucrose backbone. Deprotection of macrocyclic compounds (removal of the benzyl blocks) was possible under hydrogenolysis conditions.

A convenient route to enantiomerically pure highly oxygenated decalins from sugar allyltin derivatives

Abstract Preparation of enantiomerically pure, highly oxygenated decalins via tandem Wittig-type Diels–Alder reactions from the corresponding sugar-derived dieno-phosphoranes and/or -phosphonates and sugar aldehydes is described. Application of the phosphonates is more convenient than phosphoranes since the former can be prepared in much higher yields and react with aldehydes under milder conditions. The intermediate trienes resulting from the Wittig-type process undergo spontaneous and highly stereoselective cyclization to the cis -decalins under the reaction conditions.