(2S,3S,4E)-2--3-O-pivaloyl-4-octadecene-1,3-diol | 149933-62-0

• 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--3-O-pivaloyl-4-octadecene-1,3-diol
• 英文别名: (2S,3S,4E)-2-[N-(diphenylmethylene)amino]-3-O-pivaloyl-4-octadecene-1,3-diol；[(E,2S,3S)-2-(benzhydrylideneamino)-1-hydroxyoctadec-4-en-3-yl] 2,2-dimethylpropanoate
• CAS: 149933-62-0
• 化学式: C₃₆H₅₃NO₃
• 分子量: 547.822
• InChiKey: WMNFRPLHDFBITN-MIPDPVPASA-N

物化性质

• 沸点：
  617.6±55.0 °C(predicted)
• 密度：
  0.97±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.3
• 重原子数：
  40
• 可旋转键数：
  21
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  58.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,3S,4E)-2--3-O-pivaloyl-4-octadecene-1,3-diol 、 2,2',3,3',4',6,6'-七-O-乙酰基-alpha-D-乳糖基溴化物 在 4 A molecular sieve 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 以72%的产率得到O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1->4)-O-(2,3,6-tri-O-acetyl-β-D-glucopyranosyl)-(1->1')-(2S,3S,4E)-2--3-O-pivaloyl-4-octadecene-1,3-diol
  参考文献：
  名称：

  N-Diphenylmethylene-protected glycosyl acceptors. Selective β-O-glycosylation to form lactosyl-threo-ceramides

  摘要：

  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.

  DOI：

  10.1021/jo00068a028
• 作为产物：
  描述：

  (2S,3S,4E)-2--1-O-(tert-butyldimethylsilyl)-3-O-pivaloyl-4-octadecene-1,3-diol 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以74%的产率得到(2S,3S,4E)-2--3-O-pivaloyl-4-octadecene-1,3-diol
  参考文献：
  名称：

  N-Diphenylmethylene-protected glycosyl acceptors. Selective β-O-glycosylation to form lactosyl-threo-ceramides

  摘要：

  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.

  DOI：

  10.1021/jo00068a028

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.