78779-96-1

Upstream product

• 3102-57-6 N-((1RS,2RS)-2-hydroxy-1-hydroxymethyl-heptadec-3c-enyl)-acetamide 
• 108-24-7 acetic anhydride 
• 123-78-4 dl-threo-sphingosine 
• 3102-57-6 N-((1RS,2SR)-2-hydroxy-1-hydroxymethyl-heptadec-3c-enyl)-acetamide 
• 123-78-4 D,L-Sphingosin 
• 123-78-4 erythro-(E)-2-amino-4-octadecene-1,3-diol 
• 86120-41-4 methyl octadeca-2(E),4(E)-dien-1-oate 
• 104847-90-7 trans-2-hydroxymethyl-3-pentadec-(1E)en-1-yl-aziridine 
• 94676-99-0 N-((1RS,2SR)-2-hydroxy-1-hydroxymethyl-heptadec-3-ynyl)-acetamide 
• 114697-01-7 (+/-)-N-(4t-pentadec-1-ynyl-2r-phenyl-[1,3]dioxan-5t-yl)-acetamide 
• 114697-01-7 (+/-)-N-(4c-pentadec-1-ynyl-2r-phenyl-[1,3]dioxan-5c-yl)-acetamide 
• 94676-99-0 N-((1RS,2RS)-2-hydroxy-1-hydroxymethyl-heptadec-3-ynyl)-acetamide 
• 1097308-87-6 D-threo-sphingosine 
• 128308-04-3 N-[(1S,2R)-3-Hydroxy-2-(2-trimethylsilanyl-ethoxymethoxy)-1-(2-trimethylsilanyl-ethoxymethoxymethyl)-propyl]-acetamide 

Downstream Products

• 3102-57-6 N-((1RS,2SR)-2-hydroxy-1-hydroxymethyl-heptadec-3c-enyl)-acetamide 
• 81819-46-7 N-[(2R,4S,5R)-4-((E)-Pentadec-1-enyl)-2-phenyl-[1,3]dioxan-5-yl]-acetamide 
• 143615-69-4 (2S,3S,4E)-2-N-acetylamino-1,3-dihydroxyoctadec-4-ene 

Relevant academic research and scientific papers

A chemoenzymatic access to D- and L-sphingosines employing hydroxynitrile lyases

A chemoenzymatic access to D- or L-sphingosines is presented comprising of a total synthesis of the L-threo-isomer and formal syntheses of the other three isomers. Key to the development of a general synthetic strategy has been the use of enantiocomplementary hydroxynitrile lyases (Hnls) to yield an enantiomeric pair of starting materials. The (S)-Hnl from Hevea brasiliensis has been used to prepare L-threo-sphingosine in 14 steps and an overall 12% yield. Application of the (R)-Hnl from Prunus amygdaIus formally allows synthesis of D-threo- and D-erythro-sphingosines. (C) 2000 Elsevier Science Ltd.

A short and efficient stereoselective synthesis of all four diastereomers of sphingosine

Practical syntheses of all four stereomers of sphingosine from serine have been achieved through highly diastereoselective reduction of the N-trityl protected α′-amino enone derivative 5 with NaBH4 and reduction of the free α′-amino enone derivative 7 with Zn(BH4)2.

Stereoselective synthesis of β-amino alcohols: Practical preparation of all four stereomers of N-PMB-protected sphingosine from L- and D-serine

Serine was efficiently converted to the N-p-methoxybenzyl (PMB) protected α'-amino enone derivative 6, which was reduced with Zn(BH4)2 to the corresponding anti-β-amino alcohol in >96% de. On the other hand, N- PMB-N-Boc-protected α'-amino enone derivative 8 was reduced by NaBH4 to syn-product with a diastereoselectivity of ca. 90%.

A short enantiodivergent synthesis of D-erythro and L-threo sphingosine

A new, short (6 steps) and efficient enantiodivergent route to both D-erythro and L threo-sphingosine I and II is disclosed. The high diastereoselection (100% de) reached in the creation of the C-3 stereocenter relies on the use of a sulfoxide as chiral controlling agent in the reduction of the common precursor β-keto sulfoxide 3. The desired E-alkene of sphingosines has been constructed by the Schlosser modification of the Wittig reaction between the aldehyde 8 and the phosphonium salt 9. The reported methodology can easily be extended to the synthesis of a large number of optically pure syn and anti amino alcohols starting from commercially available amino acids.

Improved, gram scale synthesis of N,O,O-triacetyl-erythro- and threo-C18-sphingosines from serine

A formal total synthesis of all four (E)C18-sphingosine stereoisomers from serine has been carried out. This involves the thiazole-based homologation of the amino acid into a chiral 3-amino-2,4-dihydroxybutanal 1 and the Wittig olefination of 1 with the ylide from the C14 alkyl phosphonium salt 2. The photoisomerization of the resulting mixture of Z- and E-alkenes affords the target sphingosine. Thus, N,O,O-triacetyl-D-erythro C18-sphingosine 5 and the L-threo isomer 10 were prepared in 43-44% overall yield from the aldehyde (S,S)-1a and (2R,3S)-1b, respectively. The corresponding antipodal L-erythro and D-threo isomers can be prepared in the same way starting from aldehydes ent-1a and ent-1b, respectively. Conversion of the above acetyl sphingosines into the free sphingoid bases has been reported in the literature.

Aziridine-2-carboxylic acid mediated asymmetric synthesis of D-erythro-and L-threo-sphingosine from a common precursor

Short, two and three step asymmetric syntheses of L-threo- and D-erythrosphingosine (-)-6a and (-)-9a, respectively, in 58 and 31 percent overall yield were accomplished via the stereo and regioselective ring opening of N-sulfinylaziridine 2-carboxylic acid 4. Copyright

Diastereo- and Enantioselective Synthesis of L-threo- and D-erythro-Sphingosine

L-threo-sphingosine and its D-erythro isomer (1) are subunits of many glycosphingolipids, gangliosides and ceramides.This paper describes the highly diastereo- and enantioselective synthesis of both isomers (de,ee>98percent).The key steps in the synthesis are the aldol reaction of the SAMP hydrazone (S)-2 with racemic α-phenylselenylpentadecanal 3, the diastereoselective triacetoxyborohydride reduction of ketone 5 and exclusive (E) C=C double bond formation in the elimination of hydroxyl and selenyl moieties promoted by methanesulfonyl chloride.Mesylate 8 was then readily converted via the 1,3-O-acetonide-protected azidosphingosine 9 to L-threo-sphingosine.Conversion to the known 1-O,2-N-diacetyl-protected sphingosine 13 with subsequent Mitsunobu inversion of the C3-OH centre afforded the D-erythro-sphingosine epimer. - Keywords: asymmetric syntheses . alkenylations .SAMP/RAMP hydrazones . selenyl aldehydes . sphingosine

Stereoselective Synthesis of D(+)-erythro and L(-)-threo Sphingosines from Carbohydrates

Stereocontrolled syntheses of D(+)-erythro and L(-)-threo shingosines are described starting from D-xylose and D-arabinose respectively through acetylenic intermediates 3 and 4, obtained by base induced double elimination of the β-alkoxy chlorides 5 and 13. Keywords: D(+)-erythro and L(-)-threo sphingosines; base induced double elimination reaction; acetylenic alcohol

Syntheses of two pairs of enantiomeric C18-sphingosines and a palmitoyl analogue of gaucher spleen glucocerebroside

Sixteen kinds of chiral C4-epoxides [(-)-10a-d,(+)-10a-d,(-)-11a-d,(+)-11a-d], which are synthons in our synthetic strategy for complex lipids, have been prepared from (2Z)-2-butene-1,4-diol (6) by employing a Sharpless asymmetric epoxidation. By using the chiral C4-epoxides [(+)-10a,(-)-10a,(-)-11a,(+)-11a] as starting compounds, two pairs of enantiomeric (D-erythro, L-erythro, D-threo, and L-threo)-C18-sphingosines (1, 2, 3, 4) have been synthesized via a regioselective ring-opening of the epoxide ring with azide anion followed by reduction of the azide group to an amino group and a Wittig reaction. Furthermore, D-erythro-C18-sphingosine (1) has been converted to a palmitoyl analogue (5a) of Gaucher spleen glucocerebroside (5) through a reaction pathway including successive condensations with palmitic acid and D-glucose.