1,3-O-benzylidene-2-O-methanesulfonyl-D-arabino-1,2,3,4-octadecanetetrol

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: 1,3-O-benzylidene-2-O-methanesulfonyl-D-arabino-1,2,3,4-octadecanetetrol
• 英文别名: (2S,4R,5R)-4-[(R)-1-hydroxypentadecyl]-2-phenyl-1,3-dioxan-5-yl methanesulfonate；[(2S,4R,5R)-4-[(1R)-1-hydroxypentadecyl]-2-phenyl-1,3-dioxan-5-yl] methanesulfonate
• 化学式: C₂₆H₄₄O₆S
• 分子量: 484.698
• InChiKey: QLUCVCDOZFAWRP-POTDNYQPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  33
• 可旋转键数：
  17
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  90.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,3-O-benzylidene-2-O-methanesulfonyl-D-arabino-1,2,3,4-octadecanetetrol 在 盐酸 、 lithium aluminium tetrahydride 、 sodium azide 作用下， 以 四氢呋喃 、 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 64.5h， 生成 糖脂
  参考文献：
  名称：

  d-核糖和l-lyxo-植物鞘氨醇的合成：转化为相应的乳糖基神经酰胺

  摘要：

  摘要2,4-O-苄叉基-d-苏糖（2）与十四烷基溴化镁反应生成d-阿拉伯糖-和1-xylo-十八碳烯醇衍生物3a和3x，为易于分离的混合物。这些化合物分别通过区域选择性甲基化，叠氮化物置换，亚苄基裂解和叠氮化物还原分别转化为d-核糖-（1r）和1- lyxo-植物鞘氨醇（1l）。中间体叠氮基衍生物7r和7l的3,4-O-异亚丙基化得到1-O-糖基受体2-叠氮基-3,4-O-异亚丙基-d-核糖-1,3,4-十八碳三醇（8r）和2-叠氮基-3,4-O-异亚丙基-1-lyxo-1,3,4-十八碳三醇（8l）。用三氯乙酰亚氨酸酯活化的乳糖基供体9，预期的糖苷2-叠氮基-1-O-（2,3,6,2'，3'，4'，6'-庚基-O-乙酰基-β-乳糖基）- 3，

  DOI：

  10.1016/0008-6215(88)85090-0
• 作为产物：
  描述：

  在 吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 1,3-O-benzylidene-2-O-methanesulfonyl-D-arabino-1,2,3,4-octadecanetetrol
  参考文献：
  名称：

  Sphingosine and phytosphingosine from D-threose synthesis of a 4-keto-ceramide

  摘要：

  Reaction of 2,4-O-benzylidene-D-threose 3 with tetradecyl magnesium bromide furnished D-arabino- and L-xylo-octadecane-1,2,3,4-tetrols 5a,x. Regioselective oxidation of the 4-OH group gave 4-keto-D-erythro-derivative 6 which can be reduced with acetaldehyde in a SmI2-catalyzed Tishtshenko reaction to afford exclusively 5a. Regioselective 2-O-mesylation of 5a (--> 7a) and then acid catalyzed debenzylation afforded exclusively 2-O-mesyl-tetrol 9a. Reaction with NaN3 and ensuing azide reduction furnished D-ribo-C-18-phytosphingosine (2) in high overall yield. Treatment of 2-O-mesyl derivatives 7a,x with NaN3 and then with 4-nitrobenzenesulfonyl chloride in pyridine afforded 11r,l. Elimination with DBU or, alternatively, by treatment with phenylselenide and then with H2O2, gave known 1,3-O-benzylidene protected azidosphingosine 14, which can be readily converted into sphingosine (1). Transformation of 2 into ceramide 15, selective 1,3-O-silyl protection, oxidation of the 4-OH group (--> 17) and then desilylation afforded the 4-keto ceramide 18 found in a marine sponge. Reduction of 17 offers a convenient possibility for radioactive labelling of ceramides with tritium.

  DOI：

  10.1016/s0957-4166(00)86295-3

文献信息

• Copper(I)-Mediated 1,2-Metallate Rearrangements of 1-Metallated Glycals
  作者：Philip Kocieński、Krzysztof Jarowicki、Zofia Komsta、Anna Wojtasiewicz

  DOI：10.1055/s-0031-1289721

  日期：2012.3

  1,2-Metallate rearrangements involving reaction of 1-metallated glycals with organolithium reagents under copper(I) mediation give alkenylpolyol chains in 45-91% yield (19 examples). The reaction was applied to a formal synthesis of KRN7000 as well as a synthesis of a Δ5,6-ceramide derivative. 1,2-metallate rearrangement - retro-[1,4]-Brook rearrangement - 1-metallated glycals - cuprates - organolithiums

  1,2-金属盐重排涉及1-金属化的缩醛与有机锂试剂在铜（I）介导下的反应，链烯基多元醇链的收率为45-91％（19个实例）。将反应物施加到KRN7000的合成正式以及一个Δ的合成5,6- -神经酰胺衍生物。 1,2-金属盐重排-Retro- [1,4] -Brook重排-1-金属化糖-铜酸盐-有机锂-KRN7000
• Total synthesis of α-galactosyl cerebroside
  作者：Santiago Figueroa-Pérez、Richard R. Schmidt

  DOI：10.1016/s0008-6215(00)00092-6

  日期：2000.9

  A highly convergent synthetic approach was developed to obtain alpha-galactosyl cerebroside O-(alpha-D-galactopyranosyl)-2-hexacosylamino-D-ribo-1,3,4-octa decantriol, which has previously been demonstrated to have immunostimulatory activity. Known 4,6-O-benzylidene galactose was the starting material for both the required alpha-galactosyl and the phytosphingosine building blocks O-(2,3-di-O-benzyl-4

  开发了高度收敛的合成方法以获得α-半乳糖基脑苷脂O-（α-D-半乳糖吡喃糖基）-2-己糖基氨基-D-ribo-1,3,4-辛八醇，其先前已被证明具有免疫刺激活性。已知的4,6-O-亚苄基半乳糖是所需的α-半乳糖基和植物鞘氨醇构建基块O-（2,3-二-O-苄基-4,6-O-亚苄基-D-吡喃半乳糖基）的原料三氯乙酰亚胺酸酯（4）和2-O-甲磺酰基-D-阿拉伯糖基1,2,3,4-十八碳烯醇（5）。合成策略的关键步骤是使用已知的4作为供体，对1,3,4-O-未保护的植物鞘氨醇受体5进行高度区域选择性和立体选择性O-半乳糖基化。从半乳糖开始，整个合成仅需要11个合成步骤。
• Alpha-GLYCOSYL THIOLS AND alpha-S-LINKED GLYCOLIPIDS
  申请人：Zhu Xiangming

  公开号：US20100184711A1

  公开（公告）日：2010-07-22

  The present invention relates to stereoselective methods for the preparation of α-glycosyl thiols and α-S-linked glycosylceramides.

  本发明涉及用于制备α-糖基硫醇和α-S-链接糖基酰胺的立体选择性方法。
• Synthesis and immunostimulatory activity of two α-S-galactosyl phenyl-capped ceramides
  作者：Niamh Murphy、Andreea Petrasca、Niamh M. Murphy、Vincent O′Reilly、Paul Evans、Derek G. Doherty、Xiangming Zhu

  DOI：10.3998/ark.5550190.0014.224

  日期：——

  Two α-S-linked galactosylceramides carrying ω-phenyl fatty acid chains were efficiently synthesized and were shown to have in vitro stimulatory activity for human natural killer T cells.

  两种携带 ω-苯基脂肪酸链的 α-S 连接的半乳​​糖神经酰胺被有效合成，并被证明对人类自然杀伤 T 细胞具有体外刺激活性。
• Sphingosine and phytosphingosine from D-threose synthesis of a 4-keto-ceramide
  作者：Robert Wild、Richard R. Schmidt

  DOI：10.1016/s0957-4166(00)86295-3

  日期：1994.11

  Reaction of 2,4-O-benzylidene-D-threose 3 with tetradecyl magnesium bromide furnished D-arabino- and L-xylo-octadecane-1,2,3,4-tetrols 5a,x. Regioselective oxidation of the 4-OH group gave 4-keto-D-erythro-derivative 6 which can be reduced with acetaldehyde in a SmI2-catalyzed Tishtshenko reaction to afford exclusively 5a. Regioselective 2-O-mesylation of 5a (--> 7a) and then acid catalyzed debenzylation afforded exclusively 2-O-mesyl-tetrol 9a. Reaction with NaN3 and ensuing azide reduction furnished D-ribo-C-18-phytosphingosine (2) in high overall yield. Treatment of 2-O-mesyl derivatives 7a,x with NaN3 and then with 4-nitrobenzenesulfonyl chloride in pyridine afforded 11r,l. Elimination with DBU or, alternatively, by treatment with phenylselenide and then with H2O2, gave known 1,3-O-benzylidene protected azidosphingosine 14, which can be readily converted into sphingosine (1). Transformation of 2 into ceramide 15, selective 1,3-O-silyl protection, oxidation of the 4-OH group (--> 17) and then desilylation afforded the 4-keto ceramide 18 found in a marine sponge. Reduction of 17 offers a convenient possibility for radioactive labelling of ceramides with tritium.