126178-07-2

Upstream product

• 74181-34-3 2,2,-dimethyl-1,3-dioxan-5-one 
• 59983-39-0 (S)-1-amino-2-(methoxymethyl)pyrrolidine 

Downstream Products

• 126178-13-0 [(R)-4-Benzyl-2,2-dimethyl-[1,3]dioxan-(5E)-ylidene]-((S)-2-methoxymethyl-pyrrolidin-1-yl)-amine 
• 126178-04-9 [(S)-4-Benzyl-2,2-dimethyl-[1,3]dioxan-(5E)-ylidene]-((S)-2-methoxymethyl-pyrrolidin-1-yl)-amine 
• 126177-95-5 (4S)-4-[(benzyloxy)methyl]-2,2-dimethyl-1,3-dioxan-5-one 
• 943329-70-2 (4R)-4-[(benzyloxy)methyl]-2,2-dimethyl-1,3-dioxan-5-one 
• 285988-23-0 (3S,5E,2'S)-N-{2-[5-(2'-(methoxymethyl)pyrrolidin-1'-ylimino)-2,2-dimethyl-[1,3]dioxan-4-yl]ethyl}-4-methylbenzenesulfonamide 

Relevant academic research and scientific papers

Stereoselective synthesis of (+)-frontalin

Alkylation of the SAMP hydrazone of 1,3-dioxa-5-one provides a convenient way (8 steps, 40% overall yield) to synthesize frontalin in high optical purity (over 95%).

Highly diastereoselective boron-mediated anti-aldol reactions of 4-silyl substituted 2,2-dimethyl-1,3-dioxan-5-one. Diastereo- and enantioselective synthesis of protected oxopolyols

The boron enolate of 4-silylated 2,2-dimethyl-1,3-dioxan-5-one (S)-3 reacts with representative aldehydes in a highly anti diastereoselective aldol reaction to give the corresponding adducts (S,S,S)-4 in 78-93% yield with diastereoisomeric excesses of de = 96-98%. The removal of the silyl group via the triethylamine-trihydrofluoride complex leads to protected oxopolyols (S,S)-5 in good yields (64-79%) with excellent diastereomeric and enantiomeric excesses (de,ee = 96-98%). The absolute configuration was determined by X-ray structure analysis of (S,S)-5c.

Enhancing and reversing the stereoselectivity of Escherichia coli transketolase via single-point mutations

Chiral auxiliary methodology and chiral assays have been developed to establish the enantiomeric purities of erythrulose and 1,3-dihydroxypentan-2-one generated using wild-type (WT) Escherichia coli transketolase (TK). L-Erythrulose was formed in 95% ee and (3S)-1,3-dihydroxypentan-2-one in 58% ee. Since the latter compound was formed in moderate ee, TK libraries were screened to identify higher performing mutants. A colorimetric screen and chiral assay were successfully applied to a 96-well format, and new active TK mutants were identified, which gave 1,3-dihydroxypentan-2-one in high stereoselectivities. Remarkably, activesite single-point mutants were identified that were able to both enhance and reverse the stereoselectivity of TK.

Syntheses of 4-deoxy-D-fructose and enzymatic affinity study

Enantiomerically pure 4-deoxy-D-fructose has been prepared and characterised in a protected form, acidic hydrolysis of which led to an aqueous solution of 4-deoxy-D-fructose. Activities of this compound with enzymes of the glycolysis pathway involved in glucose metabolism make possible access to 4-deoxy-D-fructose-6-phosphate, 4-deoxy-D-glucose-6- phosphate and 4-deoxy-D-gluconate-6-phosphate.

Asymmetric synthesis of 4′-epi-trachycladines A and B

The first asymmetric synthesis of 4′-epi-trachycladines A and B is reported. Starting from 2,2-dimethyl-1,3-dioxan-5-one the title nucleosides were synthesised in 14 steps employing the SAMP-/RAMP-hydrazone methodology. The dioxanone-SAMP-hydrazone was first transformed into a trisubstituted derivative by a triple α-/α′-alkylation. Removal of the chiral auxiliary and subsequent reduction gave the corresponding alcohol, which could be transformed over four steps into TBS-protected 2′-C-methyl-5′-deoxy- L-lyxose. The trachycladines were then obtained via the corresponding triacetate using standard Vorbrueggen and silyl-Hilbert-Johnson conditions in an overall yield of 18-21%. Such 2′-C-branched ribonucleosides are potential agonists for adenosine receptors and play an important role in drug discovery. Georg Thieme Verlag Stuttgart.

Preparation and reactions of 2,2-dimethyl-1,3-dioxan-5-one-SAMP-hydrazone: A versatile chiral dihydroxyacetone equivalent

The SAMP-hydrazone of 2,2-dimethyl-1,3-dioxan-5-one represents a valuable chiral dihydroxyacetone equivalent. Asymmetric mono- or α,α′-bisalkylations followed by auxiliary cleavage leads to the corresponding mono- or α,α′-disubstituted, acetonide protected ketodiols in excellent diastereo- and enantiomeric excesses.

1,3-dioxan-5-one as C3-building block for the diastereo- and enantioselective synthesis of C5- To C9-deoxy sugars using the SAMP-/ RAMP-hydrazone method

The diastereo- and enantioselective synthesis of deoxy- and dideoxysugars is demonstrated using the protected dihydroxyacetone derivative 8 as a C3-building block in combination with the SAMP-/ RAMP-hydrazone method.

Enantioselective Alkylation of 2,2-Dimethyl-1,3-dioxan-5-one Using the SAMP-/RAMP-Hydrazone Method

The lithiated SAMP-hydrazone (S)-3 is used as a chiral 1,3-dihydroxyacetone-enolate equivalent C in overall enantioselective α-alkylations leading to 4-alkyl-2,2-dimethyl-1,3-dioxan-5-ones (S)-5a-i in good overall chemical yields and of high enantiomeric purity (ee = 88 - >/= 93percent.