126177-95-5

Upstream product

• 3587-60-8 Benzyloxymethyl chloride 
• 126178-07-2 (S)-(+)-1-(2,2-dimethyl-1,3-dioxan-5-ylidenamino)-2-methoxymethylpyrrolidine 
• 74181-34-3 2,2,-dimethyl-1,3-dioxan-5-one 
• 53104-32-8 (5-amino-2,2-dimethyl-1,3-dioxan-5-yl)methanol 
• 126178-05-0 [(R)-4-Benzyloxymethyl-2,2-dimethyl-[1,3]dioxan-(5E)-ylidene]-((S)-2-methoxymethyl-pyrrolidin-1-yl)-amine 

Downstream Products

• 943329-64-4 (4S,5S)-4-[(benzyloxy)methyl]-2,2,5-trimethyl-1,3-dioxan-5-ol 
• 943329-65-5 (4R)-4-[(benzyloxy)methyl]-2,2-dimethyl-5-methylene-1,3-dioxane 
• 943329-69-9 (2S,3S)-4-(benzyloxy)-1-[(tert-butyldimethylsilyl)oxy]-2-methylbutane-2,3-diol 
• 943329-68-8 (1S)-2-(benzyloxy)-1-[(2S)-2-{[(tert-butyldimethylsilyl)oxy]methyl}oxiran-2-yl]ethanol 
• 943329-67-7 (3R)-4-(benzyloxy)-1-[(tert-butyldimethylsilyl)oxy]-2-methylenebutan-3-ol 
• 943329-66-6 (3R)-4-(benzyloxy)-2-methylenebutane-1,3-diol 
• 503473-27-6 (2S,3S)-4-(benzyloxy)-2-methylbutane-1,2,3-triol 

Relevant academic research and scientific papers

Copper(II) chloride mediated racemization-free hydrolysis of α- alkylated ketone SAMP-hydrazones

Treatment of ketone SAMP-hydrazones 1a-k with an aqueous copper(II) chloride solution yields the corresponding ketones 2a-k in 52-94% yield and with high enantiomeric purities (ee = 89-99%). The cleavage conditions do not affect functionalities sensitive to oxidation and strong acids. The alkylation/cleavage protocol can be carried out in 'one-pot'.

Asymmetric synthesis of (S,S)- and (R,R)-2-methylthreitol

The asymmetric synthesis of (S,S)- and (R,R)-2-methylthreitol was carried out, starting from the SAMP or RAMP hydrazone of 2,2-dimethyl-1,3-dioxan-5-one. The protocol involves an enantioselective α-alkylation as a key step. The second stereogenic center was installed by either nucleophilic 1,2-addition or diastereoselective epoxidation with bis(acetylacetonato)oxovanadium(IV) [VO(acac)2] as catalyst. The title compounds were obtained in excellent diastereo- and enantiomeric excesses (≥98% de, 98% ee) and in good overall yields (40-61%). Georg Thieme Verlag Stuttgart.

Asymmetric synthesis of 2-amino-1,3-diols and D-erythro-sphinganine

The asymmetric synthesis of protected 2-amino-1,3-diols (S,R)-5 starting from 2,2-dimethyl-1,3-dioxan-5-one is described. The stereogenic centres are generated by α-alkylation using the SAMP/RAMP hydrazone methodology and diastereoselective reduction of t

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.

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.