Group IV.  
Chemistry of sucrose. Application of simple carbohydrates as chiral building blocks

Staff:

Anna Błońska, Ph.D. student; Maciej Cieplak, Ph.D. student; Anna Gaweł, Ph.D. student; Marta Kołaczek, Ph.D. student; Bartosz Lewandowski , Ph. D. student; Marcin Nowogródzki Ph.D. student; Zbigniew Pakulski, Ph.D.; Anna Osuch, Ph.D. student; Izabela Kościołowska, technician

Research activity

Four main topics are currently under investigation. First one is connected with the modification of sucrose molecule at the terminal positions. 2,3,4,3’4’-Penta-O-benzyl- or 1’,2,3,4,3’4’-hexa-O-benzylsucrose (both synthesized for the first time in our laboratory) serve as starting materials for the preparation of many analogs such as: ‘higher sucroses’ (homologated by 2-7 carbon atoms at either terminal position: C6, C1’ and C6’), uronic acids and amines. We are especially interested in the preparation of the crown ether analogs (also with other than oxygen heteroatoms in macrocyclic ring) with incorporated sucrose unit and to study the enantioselective complexation of chiral amines with such macrocycles. Recently we are engaged in the preparation of sucrose receptors with higher (C2) symmetry. Second topic is connected with the preparation of sugar allyltin derivatives and application of these organometallics in stereocontrolled organic synthesis. Fragmentation of these compounds (this process is connected with the opening of the sugar ring and elimination of organostannyl moiety) either with a Lewis acid or at high temperature affords useful chiral building blocks with precisely defined structure, which are used in the synthesis of highly oxygenated, optically pure derivatives of bicyclo[4.3.0]nonane and bicyclo[4.4.0]decane. Alternatively, reaction of such organometallics with aldehydes (in a process catalyzed by a Lewis acid or performed under high pressure and high temperature) affords homoallylic alcohols in enantiomerically pure form. The mechanistic aspects of all these processes are studied. Synthesis of carbocyclic sugar mimics from these synthons is carried out. Third topic is connected with the synthesis of higher carbon sugars (also C-disaccharides) having more than 10 carbon atoms in the chain (C₁₁ up to C₂₅) by coupling of two (or more) suitable activated monosaccharide subunits. Synthesis of long chain alditols, and cyclic, highly oxygenated derivatives with large-size rings is carried out. Fourth topic is connected with the synthesis of new glycosyl donors and synthesis of biologically active oligosaccharides. 

Selected scientific publications:

Reviews and monographs

1.         S. Jarosz, J. Carbohydr. Chem., 2001, 20, 93-107. Synthesis of higher carbon sugars via coupling of simple monosaccharides  – Wittig, Horner–Emmons and related methods 

2.         S. Jarosz, Formation of (Non-Anomeric) Anhydrosugars chapter 2.5. in ‘Glycoscience – Chemistry and Chemical Biology’ (vol. I-III), Springer-Verlag, 2001, 291-304.

3.         S. Jarosz, Formation of a (Non-Anomeric) Carbon-Carbon Double Bond in monosaccharides chapter 2.7. ‘Glycoscience – Chemistry and Chemical Biology’ (vol. I-III), Springer-Verlag, 2001, 365-385.

4.         S. Jarosz, A. Zamojski, Curr. Org. Chem., 2003, 7, 13-33. Carbohydrate Derivatives Containing the Carbon-Lithium and Carbon-Tin Bonds.

5.         S. Jarosz, M. Mach, Eur. J. Org. Chem., 2002, 769-780. Regio- and streoselective transformations of sucrose at the terminal positions 

6.         S. Jarosz A. Gaweł, Eur. J. Org. Chem., 2005, 3415-3432. Sugar allyltins. Preparation and application in organic synthesis

7.         S. Jarosz, A. Listkowski, Current Organic Chem., 2006, 10, 643-662. Sugar derived crown ethers and their analogs: synthesis and properties

8.         Y. Queneau, S. Jarosz, B. Lewandowski, J. Fitremann, Adv. Carbohydr. Chem. Biochem., 2007, 61, 221-300. Sucrose Chemistry and Applications of Sucrochemicals  

Original articles

1.         S. Jarosz, M. Mach, J. Chem. Soc., Perkin Trans. 1, 1998, 3943-3948. Phosphonate versus phosphorane method in the synthesis of higher carbon sugars Preparation of D-erythro-L-manno-D-gluco-dodecitol

2.         S. Jarosz, S. Skóra, Tetrahedron: Asymmetry, 2000, 11, 1425-1432. A convenient route to enantiomerically pure bicyclo[4.3.0]nonanes from sugar allyltins 

3.         S. Jarosz, S. Skóra, Tetrahedron: Asymmetry, 2000, 11, 1433-1448. A convenient route to enantiomerically pure highly oxygenated decalines from sugar allyltin derivatives.

4.         Z. Pakulski, Synthesis 2003, 2074-2078. Glycosylation in ionic liquids

5.         S. Jarosz,  A. Listkowski, J. Carbohydr. Chem., 2003, 22, 753-763. Synthesis of macrocyclic derivatives containing sucrose unit

6.         S. Jarosz, K. Szewczyk, A. Zawisza, Tetrahedron: Asymmetry, 2003, 14, 1715-1723. Synthesis and Thermal Stability of Secondary Sugar Allyltin Derivatives.

7.         S. Jarosz, A. Listkowski, B. Lewandowski, Z. Ciunik, A. Brzuszkiewicz, Tetrahedron, 2005, 61, 8485-8492. Macrocyclic receptors containing sucrose skeleton

8.         S. Jarosz, M. Nowogródzki, J. Carbohydr. Chem., 2006, 25, 139-149; Approach Towards Highly Oxygenated cis-Decalins From Sugar Allyltins

9.         S. Jarosz, M. Nowogródzki, M. Kołaczek, Tetrahedron: Asymmetry, 2007, 18,  2674-2679; Synthesis of highly oxygenated carbocyclic derivatives: decalins and cyclohexanes from sugar allyltins

10.       M. Piekutowska, Z. Pakulski, Carbohydr. Res. 2008, 343, 785-792; Synthesis of S-glycosyl thiophosphates, thiophosphonates and thiophosphinates by the Michaelis-Arbuzov rearrangement of anomeric thiocyanates

11.       S. Jarosz, B. Lewandowski, Carbohydr. Res. 2008, 343, 965 - 969; Synthesis and complexing properties towards ammonium cation of aza-coronand analogues containing sucrose molecule

12.       S. Jarosz, B. Lewandowski, A. Listkowski, Synthesis, 2008, 913 – 916; Towards sucrose macrocycles with higher symmetry via a click chemistry’ route