1,3,4,5-Tetra-O-benzyl-6-O-(tert-butyldimethylsilyl)-L-galactitol | 158535-90-1

• 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: 1,3,4,5-Tetra-O-benzyl-6-O-(tert-butyldimethylsilyl)-L-galactitol
• 英文别名: 2,3,4,6-tetra-O-benzyl-1-O-tert-butyldimethylsilyl-D-galactitol；(2R,3S,4R,5S)-6-[tert-butyl(dimethyl)silyl]oxy-1,3,4,5-tetrakis(phenylmethoxy)hexan-2-ol
• CAS: 158535-90-1
• 化学式: C₄₀H₅₂O₆Si
• 分子量: 656.935
• InChiKey: DOJOYGLEUXHRRF-ZSZOPTSRSA-N

物化性质

• 沸点：
  702.9±60.0 °C(predicted)
• 密度：
  1.091±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.34
• 重原子数：
  47
• 可旋转键数：
  20
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,3,4,5-Tetra-O-benzyl-6-O-(tert-butyldimethylsilyl)-L-galactitol 在 草酰氯 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 、 叔丁醇 为溶剂， 反应 4.75h， 生成 tert-Butyl-dimethyl-((Z)-(2S,3S,4S)-2,3,4-tris-benzyloxy-5-benzyloxymethyl-6-bromo-hex-5-enyloxy)-silane
  参考文献：
  名称：

  O-连接的糖肽的等排物的合成。

  摘要：

  [反应：见正文]描述了由D-半乳糖合成亲电的碳环半乳糖等效物的途径。该策略将闭环复分解与格鲁布斯的第二代催化剂作为关键步骤。半乳糖衍生的亲电试剂以S（N）2的方式与N-Boc-半胱氨酸甲酯反应，以提供α-半乳糖基丝氨酸等排异构体。该方法扩展到糖肽等排体的合成。

  DOI：

  10.1021/ol0490779
• 作为产物：
  描述：

  Α-D-乳酸吡喃糖苷甲酯 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 硫酸 、 sodium hydride 、 溶剂黄146 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 1,3,4,5-Tetra-O-benzyl-6-O-(tert-butyldimethylsilyl)-L-galactitol
  参考文献：
  名称：

  Synthesis and Analysis of Substrate Analogues for UDP-Galactopyranose Mutase:  Implication for an Oxocarbenium Ion Intermediate in the Catalytic Mechanism

  摘要：

  UDP-D-galactofuranose ( 2), which is essential for both cell growth and virulence in many pathogenic microorganisms, is converted from UDP-D-galactopyranose (UDP-Galp, 1) by the flavin adenine dinucleotide (FAD)-dependent enzyme UDP-galactopyranose mutase (UGM). Here, we report the synthesis of UDP-GalOH ( 13) and show it as an inhibitor for UGM with a binding affinity similar to that of 1. These results are more consistent with a mechanism involving an oxocarbenium ion intermediate in UGM catalysis.

  DOI：

  10.1021/ol0631408

文献信息

• Synthesis of Protected Carbohydrate Derivatives Through Homologation of Threose and Erythrose Derivatives with Chiral .gamma.-Alkoxy Allylic Stannanes
  作者：James A. Marshall、Boris M. Seletsky、George P. Luke

  DOI：10.1021/jo00091a034

  日期：1994.6

  Additions of the gamma-alkoxy allylic stannanes (S)-1 and (R)-1 and the racemate (RS)-1 to the threose and erythrose aldehyde derivatives 6 and 15 in the presence of BF3.OEt(2) or MgBr2.OEt(2) were examined in order to establish stereochemical preferences. It was found that (S)-1 and aldehyde 6 afforded the syn,anti,syn adduct 7 in the BF3-promoted reaction, while (R)-1 and 6 gave the syn,syn,syn adduct 8 under MgBr2 conditions. Likewise, (S)-1 and aldehyde 15 yielded the syn,anti,anti adduct 16 with BF3, whereas (R)-1 and 15 led to the syn,syn,anti adduct 17 with MgBr2. The MgBr2-promoted reactions showed sufficient rate differences between the matched and mismatched stannanes to allow the use of racemic stannane (RS)-1 in just over 2-fold excess, whereupon the matched adducts 8 and 17 were favored by greater than 9:1 over the mismatched adducts. The major adducts 7, 8, 16, and 17 were converted to the hexose derivatives 21, 30/31, 34, and 39 by ozonolysis, selective deprotection, and refunctionalization. Adducts 16 and 17 were dihydroxylated with OsO4-NMO to the deoxyoctose precursors 40/41 and 42/43.
• Synthesis of an Isostere of an O-Linked Glycopeptide
  作者：Lisa J. Whalen、Randall L. Halcomb

  DOI：10.1021/ol0490779

  日期：2004.9.1

  route for the synthesis of an electrophilic, carbocyclic galactose equivalent from D-galactose is described. The strategy utilizes ring-closing metathesis with Grubbs's second-generation catalyst as the key step. The galactose-derived electrophile reacted in an S(N)2 fashion with N-Boc-cysteine methyl ester to provide an alpha-galactosylserine isostere. The method was extended to the synthesis of a glycopeptide

  [反应：见正文]描述了由D-半乳糖合成亲电的碳环半乳糖等效物的途径。该策略将闭环复分解与格鲁布斯的第二代催化剂作为关键步骤。半乳糖衍生的亲电试剂以S（N）2的方式与N-Boc-半胱氨酸甲酯反应，以提供α-半乳糖基丝氨酸等排异构体。该方法扩展到糖肽等排体的合成。
• Synthesis and Analysis of Substrate Analogues for UDP-Galactopyranose Mutase:  Implication for an Oxocarbenium Ion Intermediate in the Catalytic Mechanism
  作者：Kenji Itoh、Zhishu Huang、Hung-wen Liu

  DOI：10.1021/ol0631408

  日期：2007.3.1

  UDP-D-galactofuranose ( 2), which is essential for both cell growth and virulence in many pathogenic microorganisms, is converted from UDP-D-galactopyranose (UDP-Galp, 1) by the flavin adenine dinucleotide (FAD)-dependent enzyme UDP-galactopyranose mutase (UGM). Here, we report the synthesis of UDP-GalOH ( 13) and show it as an inhibitor for UGM with a binding affinity similar to that of 1. These results are more consistent with a mechanism involving an oxocarbenium ion intermediate in UGM catalysis.