1,6-anhydro-3,4-O-isopropylidene-1-thio-D-mannitol | 63700-03-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻庚烷
• 英文名称: 1,6-anhydro-3,4-O-isopropylidene-1-thio-D-mannitol
• 英文别名: 1,6-dideoxy-3,4-O-isopropylidene-1,6-thio-D-mannitol；3,6-dihydroxy-4,5-di-O-isopropylidenethiepane；(+/-)-(3aS,4R,8S,8aS)-2,2-dimethylhexahydrothiepino[4,5-d][1,3]dioxole-4,8-diol；(3aR,4S,8S,8aR)-2,2-dimethylhexahydrothiepino[4,5-d][1,3]dioxole-4,8-diol；(3R,4S,5S,6R)-3,6-dihydroxy-4,5-O-isopropylidene-thiepane；(3aR,4S,8S,8aR)-2,2-dimethyl-3a,4,5,7,8,8a-hexahydrothiepino[4,5-d][1,3]dioxole-4,8-diol
• CAS: 63700-03-8
• 化学式: C₉H₁₆O₄S
• 分子量: 220.29
• InChiKey: AMTZCFFTUVSCSK-WCTZXXKLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  84.2
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,6-anhydro-3,4-O-isopropylidene-1-thio-D-mannitol 在 吡啶 、 三氟乙酸 作用下， 以 水 为溶剂， 反应 2.0h， 生成 2,3,4,5-tetra-O-acetyl-1,6-anhydro-1-thio-D-mannitol
  参考文献：
  名称：

  具有抗血栓形成活性的4-氰基和4-硝基苯基的1,6-二硫代-D-甘露糖苷，L-氨基-和D-葡萄糖苷的合成。

  摘要：

  1,6-脱水-3,4-O-异亚丙基-1-硫代-D-甘露糖醇转化为亚砜，水解，乙酰化和随后的Pummerer重排后得到五-O-乙酰基-1-硫代-D-甘露糖庚糖异构体，收率优异。该异头混合物被用作供体，分别在三氟化硼醚化物和三甲基甲硅烷基三氟甲磺酸盐的存在下进行4-硝基-和4-氰基苯硫醇的糖基化反应，以高产率产生相应的硫代庚糖苷。使用1,6-脱水-3,4-O-异亚丙基-1-硫代-L-糖醇作为起始原料，将相同的策略应用于相应的L-亚氨基硫代糖苷的合成。五-O-乙酰基-D-葡糖硫庚糖供体不能以相同的方式合成，因为相应的四-O-乙酰基-1的Pummerer反应 6-硫代脱水-1-硫代-D-葡萄糖醇亚砜导致了相应的L-古洛糖基和D-葡糖硫代庚糖异构体的不可分离的混合物。因此，D-葡萄糖二乙基二硫缩醛通过其2,3,4,5-四-O-乙酰基-6-S-乙酰基衍生物被转化为其6-硫代-庚糖和-呋喃糖过乙酸酯的端

  DOI：

  10.1016/s0008-6215(02)00128-3
• 作为产物：
  描述：

  1,2;5,6-dianhydro-3,4-O-isopropylidene-D-mannitol 在 sodium sulfide 作用下， 以 乙醇 为溶剂， 以60%的产率得到1,6-anhydro-3,4-O-isopropylidene-1-thio-D-mannitol
  参考文献：
  名称：

  硫糖作为糖苷酶的弱抑制剂的合成

  摘要：

  一系列对映体纯的硫糖（1,6-dideoxy-1,6-thio-D-甘露醇或L-iditol，1,5-dideoxy-1,5-thio-L-gulitol或D-葡萄糖醇和2,5 -二脱氧-2，5-硫代-L-ID醇或D-甘露醇，及其相应的亚砜或砜）是通过C 2对称双环氧化物的硫环化合成的，随后在少数情况下随后进行环异构化。这些化合物已被评估为几种糖苷酶（α-和β-D-葡萄糖苷酶，α-D-甘露糖苷酶和α-L-岩藻糖苷酶）的抑制剂。

  DOI：

  10.1016/s0040-4020(97)10096-5

文献信息

• A General Procedure to Enantiopure Conduritols: Sulfur-Mediated Synthesis of (+)-Conduritol B and (−)-Conduritol F Derivatives and of (−)-Conduritol E and F
  作者：Vanda Cerè、Giuseppe Mantovani、Francesca Peri、Salvatore Pollicino、Alfredo Ricci

  DOI：10.1016/s0040-4020(00)00011-9

  日期：2000.2

  demonstrated the generality of a simple procedure, synthesizing enantiomerically pure (+)-conduritol B and (−)-conduritol F derivatives, starting from d-mannitol and d-sorbitol, respectively. This method, slightly modified, can also be applied to the synthesis of unprotected conduritols: (−)-conduritol E and (−)-conduritol F were obtained.

  我们已经证明了简单方法的一般性，它们分别从d-甘露醇和d-山梨糖醇合成对映体纯的（+）-conduritol B和（-）-conduritol F衍生物。稍加修改后的该方法也可用于合成未保护的松露醇：（-）-松露醇E和（-）-松露醇F。
• Synthesis, Chromatographic Separation, Vibrational Circular Dichroism Spectroscopy, and ab Initio DFT Studies of Chiral Thiepane Tetraol Derivatives
  作者：Vanda Cerè、Francesca Peri、Salvatore Pollicino、Alfredo Ricci、Frank J. Devlin、Philip J. Stephens、Francesco Gasparrini、Romina Rompietti、Claudio Villani

  DOI：10.1021/jo048629y

  日期：2005.1.1

  Optically pure enantiomers of the chiral tetrahydroxythiepane derivative 3,6-dihydroxy-4,5-O-isopropylidene-thiepane (3) are obtained using a novel protocol in which a library of all possible stereoisomers of 3 is synthesized, followed by two-step stereoselective chromatography, using, first, conventional achiral and, then, chiral stationary phases. Configurational and conformational analysis of 3 are carried out using Vibrational Circular Dichroism (VCD) spectroscopy in conjunction with ab initio DFT calculations. The absolute configuration of 3 is shown to be 3R,4S,5R,6R-(+)/ 3S,4R,5S,6S-(-).
• Thiosugars from D-mannitol
  作者：Myrielle Fuzier、Yves Le Merrer、Jean-Claude Depezay

  DOI：10.1016/0040-4039(95)01273-k

  日期：1995.9

  Enantiomerically pure thiosugars, with a thiepan, tetrahydrothiopyrum or tetrahydrothiophene backbone, have been synthesized by thio-heterocyclization of enantiopure C-2-symmetric bis-epoxides and possibly ring contraction.
• Catalytic and enantioselective bromoetherification of olefinic 1,3-diols: mechanistic insight
  作者：Zhihai Ke、Chong Kiat Tan、Yi Liu、Keefe Guang Zhi Lee、Ying-Yeung Yeung

  DOI：10.1016/j.tet.2015.09.016

  日期：2016.5

  How can high enantioselectivity be achieved when the racemic background reaction proceeds at a rate comparable to that of the catalytic asymmetric reaction? We attempted to rationalize this counterin-tuitive observation by studying the effect of (1) catalyst structure, (2) temperature and addition sequence of components, (3) catalyst loading, and (4) Bronsted acid additives. In the course of our investigation, it was found that increasing the amount of catalyst used led to inhibition of the stoichiometric reaction. Olefinic 1,3-diol 1, 5 mol % of catalyst 3a, 1 equiv of MsOH, and NBS were added at low temperature in a specific sequence to provide the best performance for the enantioselective bromoetherification. (C) 2015 Elsevier Ltd. All rights reserved.
• Regio- and Stereospecific Me₃SiI-Promoted Intramolecular Displacement of Hydroxy Group by Sulfide. 2. Polyhydroxylated Thiepane Ring Contraction to Thiolane or Thiane Derivatives. Synthesis of Enantiopure Polyalcohols¹
  作者：Vanda Cerè、Francesca Peri、Salvatore Pollicino

  DOI：10.1021/jo9711448

  日期：1997.11.1