(2S,3S,4E)-2--1-O-(tert-butyldimethylsilyl)-4-octadecene-1,3-diol | 143428-49-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3S,4E)-2--1-O-(tert-butyldimethylsilyl)-4-octadecene-1,3-diol
• 英文别名: (E,2S,3S)-2-(benzhydrylideneamino)-1-[tert-butyl(dimethyl)silyl]oxyoctadec-4-en-3-ol
• CAS: 143428-49-3
• 化学式: C₃₇H₅₉NO₂Si
• 分子量: 577.966
• InChiKey: GUENASBJNUCUBF-XFCBJZLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.53
• 重原子数：
  41
• 可旋转键数：
  21
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  41.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3S,4E)-2--1-O-(tert-butyldimethylsilyl)-4-octadecene-1,3-diol 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 生成 L-苏型-鞘氨醇C-18
  参考文献：
  名称：

  Aluminoxy acetals from .alpha.-amino esters: chirality transfer via sequential addition of hydride and C-nucleophiles. 2-Amino alcohols and sphingosines

  摘要：

  The reaction of alpha-imino esters (O'Donnell's Schiff bases) with aluminum hydrides to produce acetal-like intermediates and subsequent reaction with carbon nucleophiles has been studied. Treatment of optically pure imine-protected amino esters with iBu2AlH or iBuAlH.Bu3Al, followed by RMgX or RLi provided threo-2-amino alcohols in high yield (73-85%) and excellent ''syn'' stereoselectivity (8:1 to >20.1, threo or like product preferred). Use of nonpolar solvents (CH2Cl2-hexane) provided the highest stereoselectivities. Use of the less-reactive iBu2AlH.iBu3Al complex lowered the amount of undesired primary alcohol products observed. Thermally labile aluminoxy acetal intermediates were observed by H-1 NMR and were trapped with N-(trimethylsilyl)imidazole to produce relatively stable monosilyl acetals (mixed acetals). Alanine-derived Schiff bases 2a-e showed a correlation between the steric bulk of the ester and threo selectivity The presence of THF reduced this correlation, suggesting the C-nucleophile addition involves a Lewis acid-assisted S(N)2-like displacement of the aluminoxy acetal or displacement of a tight-ion pair. In addition to the synthesis of optically pure arylethanolamines 6a-d from representative amino acids, threo-sphingosines 8a-d were synthesized from L-serine-derived Schiff base 4b, and 1-deoxy-threo-sphingosines 9a-d were synthesized from L-alanine in a similar fashion. Experimental details are provided.

  DOI：

  10.1021/jo00046a032
• 作为产物：
  描述：

  N-(二苯基亚甲基)-L-丝氨酸甲酯 在 咪唑 、 三异丁基铝 、 二异丁基氢化铝 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 26.25h， 生成 (2S,3S,4E)-2--1-O-(tert-butyldimethylsilyl)-4-octadecene-1,3-diol
  参考文献：
  名称：

  Aluminoxy acetals from .alpha.-amino esters: chirality transfer via sequential addition of hydride and C-nucleophiles. 2-Amino alcohols and sphingosines

  摘要：

  The reaction of alpha-imino esters (O'Donnell's Schiff bases) with aluminum hydrides to produce acetal-like intermediates and subsequent reaction with carbon nucleophiles has been studied. Treatment of optically pure imine-protected amino esters with iBu2AlH or iBuAlH.Bu3Al, followed by RMgX or RLi provided threo-2-amino alcohols in high yield (73-85%) and excellent ''syn'' stereoselectivity (8:1 to >20.1, threo or like product preferred). Use of nonpolar solvents (CH2Cl2-hexane) provided the highest stereoselectivities. Use of the less-reactive iBu2AlH.iBu3Al complex lowered the amount of undesired primary alcohol products observed. Thermally labile aluminoxy acetal intermediates were observed by H-1 NMR and were trapped with N-(trimethylsilyl)imidazole to produce relatively stable monosilyl acetals (mixed acetals). Alanine-derived Schiff bases 2a-e showed a correlation between the steric bulk of the ester and threo selectivity The presence of THF reduced this correlation, suggesting the C-nucleophile addition involves a Lewis acid-assisted S(N)2-like displacement of the aluminoxy acetal or displacement of a tight-ion pair. In addition to the synthesis of optically pure arylethanolamines 6a-d from representative amino acids, threo-sphingosines 8a-d were synthesized from L-serine-derived Schiff base 4b, and 1-deoxy-threo-sphingosines 9a-d were synthesized from L-alanine in a similar fashion. Experimental details are provided.

  DOI：

  10.1021/jo00046a032

文献信息

• N-Diphenylmethylene-protected glycosyl acceptors. Selective β-O-glycosylation to form lactosyl-threo-ceramides
  作者：Matt A. Peterson、Robin Polt

  DOI：10.1021/jo00068a028

  日期：1993.7

  A series of N-diphenylmethylene-protected sphingosine derivatives was synthesized (e.g 3a,b and 9a,b). These compounds are efficient glycosyl acceptors and were shown to undergo highly beta-selective glycosylation using a modification of the Koenigs-Knorr reaction previously used in this laboratory for the synthesis of O-linked glycopeptides (none of the alpha-anomers were detected by either H-1 or C-13 NMR).1 The N-diphenylmethylene (Schiff base) protection imparts a favorable intramolecular hydrogen-bonding pattern (Ph2C=N:-->H-O:). This intramolecular hydrogen-bonding enhances the nucleophilicity of the glycosyl acceptor relative to glycosyl acceptors with more conventional N-protection (i.e. Cbz, Boc, acyl etc.). The enhanced nucleophilicity allowed the glycosylation to be carried out under mild conditions (AgOTfl, CH2Cl2, rt overnight), and provided the corresponding beta-glycosphingolipids 4a-c and 11a-d in excellent chemical yield (approximately 70%). After glycosylation, selective acid-catalyzed hydrolysis of the Schiff base protecting group was accomplished without cleavage of the glycosidic bond or the carbohydrate acetate protection. N-Acylation with palmitoyl chloride, followed by Zemplen deacetylation (cat. NaOMe in MeOH), provided the two threo-beta-lactosylceramide analogues 7a and 7b. These analogues possess the unnatural threo-configuration in the ceramide moiety and may prove useful in studies of the biosynthesis and cell surface composition of more complex glycosphingolipids.
• Aluminoxy acetals from .alpha.-amino esters: chirality transfer via sequential addition of hydride and C-nucleophiles. 2-Amino alcohols and sphingosines
  作者：Robin Polt、Matt A. Peterson、Lynn DeYoung

  DOI：10.1021/jo00046a032

  日期：1992.9

  The reaction of alpha-imino esters (O'Donnell's Schiff bases) with aluminum hydrides to produce acetal-like intermediates and subsequent reaction with carbon nucleophiles has been studied. Treatment of optically pure imine-protected amino esters with iBu2AlH or iBuAlH.Bu3Al, followed by RMgX or RLi provided threo-2-amino alcohols in high yield (73-85%) and excellent ''syn'' stereoselectivity (8:1 to >20.1, threo or like product preferred). Use of nonpolar solvents (CH2Cl2-hexane) provided the highest stereoselectivities. Use of the less-reactive iBu2AlH.iBu3Al complex lowered the amount of undesired primary alcohol products observed. Thermally labile aluminoxy acetal intermediates were observed by H-1 NMR and were trapped with N-(trimethylsilyl)imidazole to produce relatively stable monosilyl acetals (mixed acetals). Alanine-derived Schiff bases 2a-e showed a correlation between the steric bulk of the ester and threo selectivity The presence of THF reduced this correlation, suggesting the C-nucleophile addition involves a Lewis acid-assisted S(N)2-like displacement of the aluminoxy acetal or displacement of a tight-ion pair. In addition to the synthesis of optically pure arylethanolamines 6a-d from representative amino acids, threo-sphingosines 8a-d were synthesized from L-serine-derived Schiff base 4b, and 1-deoxy-threo-sphingosines 9a-d were synthesized from L-alanine in a similar fashion. Experimental details are provided.