81577-58-4

Upstream product

• 80995-79-5 (2R,4S,4aS,6S,8aR)-2-((2S,4S,5R)-5-Hydroxy-2-phenyl-[1,3]dioxan-4-yl)-6-phenyl-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-ol 
• 99274-32-5 2,4-O-benzylidene-D-threose 
• 3006-41-5 (4aR,7R,8R,8aR)-2-phenylhexahydropyrano[3,2-d][1,3]dioxine-6,7,8-triol 
• 488-82-4 D-Arabitol 
• 100-52-7 benzaldehyde 
• 80924-06-7 1,3-O-benzylidene D-arabitol 
• 30688-66-5 4,6-O-benzylidene-D-glucopyranose 
• 1125-88-8 benzaldehyde dimethyl acetal 

Downstream Products

• 92206-12-7 (2R,3S)-2,4-bis(benzyloxy)butane-1,3-diol 
• 1426147-48-9 C₁₉H₂₆O₅ 
• 1426147-60-5 C₁₆H₂₂O₅ 
• 652979-92-5 1,3-O-benzylidene-D-threitol 4-(t-butyldimethylsilyl) ether 
• 81577-65-3 methyl (2S,4S,5R)-5-Hydroxy-2-phenyl-1,3-dioxane-4-carboxylate 

Relevant academic research and scientific papers

Tertiary Amine Promoted Asymmetric Aldol Reaction of Aldehydes

The direct asymmetric self-aldol reactions of various α-oxyaldehydes catalyzed by tertiary amines have been demonstrated. By using 10 mol-% of quinine catalyst, dimerization products have been prepared in high yields, with good anti-diastereocontrol, and up to 80% ee. The presented enolate-mediated synthesis of protected tetrose sugars has never been accomplished before by chiral tertiary amine organocatalysts.

Synthesis of an oxidation-stable analogue of cyclic pyranopterin monophosphate (cPMP)

Molybdenum cofactor (Moco) deficiency is a lethal hereditary metabolic disease. A recently developed therapy requires continuous intravenous supplementation of the biosynthetic Moco precursor cyclic pyranopterin monophosphate (cPMP). The limited stability of the latter natural product, mostly due to oxidative degradation, is problematic for oral administration. Therefore, the synthesis of more stable cPMP analogues is of great interest. In this context and for the first time, the synthesis of a cPMP analogue, in which the oxidation-labile reduced pterin unit is replaced by a pyrazine moiety, was achieved starting from the chiral pool materials D-galactose or D-arabitol. Our synthesis, 13 steps in total, includes the following key transformations: i) pyrazine lithiation, followed by acylation; ii) closure of the pyrane ring by nucleophilic aromatic substitution; and iii) introduction of phosphate.

The dioxanone approach to (2S,3R)-2-C-methylerythritol 4-phosphate and 2,4-cyclodiphosphate, and various MEP analogues

(Chemical Equation Presented) Efficient syntheses of the non-mevalonate pathway intermediates 2-C-methylerythritol 4-phosphate (MEP) and 2-C-methylerythritol 2,4-cyclodiphosphate (ME-2,4-cycloPP), as well as the parent tetrol 2-C-methylerythritol, in enantiopure form from (2S,4R)-cis-2-phenyl-4-tert-butyldimethylsilyloxy-1,3-dioxan-5-one are reported. The 2S configuration of the C-methyl group was installed by highly axial-face selective addition of CH3MgBr (20:1) to the chiral dioxanone carbonyl group. Primary selective monophosphorylation and 2,4-bis-phosphorylation, followed by desilation and hydrogenolysis to the free mono-and diphosphates, and, in the latter case, cyclization to form the eight-membered phosphoryl anhydride, afforded MEP and ME-2,4-cycloPP in good yields. The C2 epimeric analogues, 2-C-methylthreitol and its 4-phosphate, were accessed by LiAlH 4 reduction of the cis,cis epoxide of (2S,4R)-4-tert- butyldimethylsilyloxymethyl-5-methylene-2-phenyl-1,3-dioxane, primary-selective phosphorylation, and cleavage of the silyl, benzylidene, and benzyl protecting groups. Regioselective cleavage of the acetal ring of 1,3-benzylidene 2-C-methylerythritol silyl ether by ozonolysis afforded a 1,2,3-triol 3-monobenzoate intermediate that was converted to the novel amino sugar, 1-amino-1-deoxy-2-C-methylerythritol.

Stereochemistry of the [2+2] cycloaddition of chlorosulfonyl isocyanate to chiral alkoxyallenes derived from 1,3-alkylidene-L-erythritol and -D-threitol

The [2+2] cycloaddition of chlorosulfonyl isocyanate to alkoxyallenes derived from ethylidene and benzylidene erythritols and threitols proceeds with a moderate asymmetric induction in the case of the erythritols and with a very low induction in the case of threitols. This indicates that the erythritol derivatives may exist in solution in one predominant conformation while the threitol derivatives behave as a conformational ensemble. The conformations of alkoxyallenes were studied with variety of NMR techniques as well as using ab initio calculations. The results thus obtained were in a full agreement with our predictions based on the stereoselectivity of cycloaddition. The azetidinones obtained by the cycloaddition were subjected to intramolecular alkylation at the nitrogen atom to provide the corresponding tricyclic cephams. The absolute configurations of the resultant azetidinones and cephams were assigned using NMR and CD spectroscopy. Wiley-VCH Verlag GmbH & Co, KGaA, 69451 Weinheim, Germany, 2005.

Synthesis of Enantiopure 2-C-Methyl-D-erythritol 4-Phosphate and 2,4-Cyclodiphosphate from D-Arabitol

(Equation presented) Two key intermediates of the newly discovered mevalonate-independent pathway for isoprenoid biosynthesis were prepared. Optically pure 2-C-methyl-D-erythritol 4-phosphate and 2,4-cyclodiphosphate were chemically synthesized from D-arabitol using a convenient benzylidene and tert-butyldimethylsilyl protection of polyhydroxylated intermediates. The new scheme offers a straightforward route to analogues and labeled forms.

Reactions of Benzylidene-D-tetroses

Silver oxide catalyzed methylations of the dimeric benzylidene-D-threose 3 result in blocking of the acetal function with formation of either the monomethyl acetal 4 or the dimeric glycoside 6.Under varied conditions methylation is achieved with predomina