1,2:5,6-di-O-isopropylidene-D-glucofuranose (S_S)-methanesulfinate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2:5,6-di-O-isopropylidene-D-glucofuranose (S_S)-methanesulfinate
• 英文别名: [(3aR,5R,6S,6aR)-5-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl] (R)-methanesulfinate
• 化学式: C₁₃H₂₂O₇S
• 分子量: 322.379
• InChiKey: UOAQMPDRBKTTFV-UVPZNDOPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  91.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,2:5,6-di-O-isopropylidene-D-glucofuranose (S_S)-methanesulfinate 以95%的产率得到
  参考文献：
  名称：

  Noureddine Khiar*{1}, Inmaculada Fernandez*, and Felipe Alcudia, Tetrahedron Lett, 35 (1994) N 31, S 5719-5722

  摘要：

  DOI：
• 作为产物：
  描述：

  1,2:5,6-diacetone-D-glucose 、 甲烷亚磺酰氯化物 在 吡啶 作用下， 以 四氢呋喃 为溶剂， 生成 1,2:5,6-di-O-isopropylidene-D-glucofuranose (S_S)-methanesulfinate
  参考文献：
  名称：

  Bis-sulfoxides as ligands for platinum complexes

  摘要：

  In this article, we describe two new platinum(II) complexes incorporating C(2)-symmetric enantiopure bis-sulfoxides ligands. The originality of these structures resides in the one-carbon tether between the two sulfoxide functions. X-ray structures show that coordination takes place through both sulfur atoms giving birth to intriguing platina-cyclobutane systems. We anticipate that these complexes should find uses in asymmetric catalysis. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.04.023

文献信息

• Asymmetric synthesis of optically pure tert-butyl sulfoxides using the “DAG methodology”
  作者：Noureddine Khiar、Inmaculada Fernández、Felipe Alcudia

  DOI：10.1016/s0040-4039(00)77288-1

  日期：1994.8

  excess. These sulfinates were transformed into various enantiomerically pure tert-butyl sulfoxides by reaction with different Grignard reagents. Additionally, the reaction of tert-butylmagnesium chloride with (+)-(R)- and (−)-(S)-methanesulfinates of DAG has been found to occur with complete inversion of configuration and not with retention as previously reported.

  双丙酮-D-葡萄糖（DAG）在NEt 3和Py的存在下与t- BuSOCl反应，分别以高的非对映异构体过量分别生成（-）-（S）-和（+）-（R）-叔丁亚磺酸盐。通过与不同的格氏试剂反应，将这些亚磺酸盐转化为对映体纯的叔丁基亚砜。另外，已经发现叔丁基氯化镁与DAG的（+）-（R）-和（-）-（S）-甲亚磺酸盐的反应在构型完全反转而不保留的情况下发生，如先前报道的。
• General Method for Asymmetric Synthesis of α-Methylsulfinyl Ketones:  Application to the Synthesis of Optically Pure Oxisuran and Bioisosteres
  作者：H. El Ouazzani、N. Khiar、I. Fernández、F. Alcudia

  DOI：10.1021/jo961038q

  日期：1997.1.1

  compounds led to some epimerization at sulfur. This loss of chirality was circumvented by reacting the alpha-lithio derivatives of the N,N-dimethylhydrazones derived from these ketones with either the (R)- or the (S)-methanesulfinate of diacetone D-glucose, to yield the corresponding alpha-(methylsulfinyl)methylhydrazones, with complete inversion of chirality at sulfur. Hydrolysis of the resulting

  记载了合成的免疫抑制药奥沙苏兰[1，（甲基亚磺酰基）甲基2-吡啶基酮]的首次不对称合成。使用DAG方法进行关键的缩合步骤，以光学纯净的形式高效合成了两种对映异构体。尝试将芳基甲基酮的金属烯醇盐与手性亚磺酰基化合物偶合，导致在硫上有些差向异构。通过使由这些酮衍生的N，N-二甲基hydr的α-硫代衍生物与双丙酮D-葡萄糖的（R）-或（S）-甲亚磺酸盐反应，制得相应的α- （甲基亚磺酰基）甲基hydr，在硫上具有完全的手性反转。用氯化铜（II）水解所得，得到光学纯形式的1。通过制备旋光的奥苏兰类似物2-4证明了该方法的普遍性，其中吡啶基部分分别被苯基，呋喃基和噻吩基部分取代。在研究β-酮亚砜的外消旋混合物所建立的条件下，使用手性位移试剂通过质子NMR光谱法测定这些产物的光学纯度。
• Stereoselective synthesis of 3-alkylsulfinylmethylisoxazolines and their use as chiral nucleophiles in the chain elongation of 2,3-O-isopropylidene-d-glyceraldehyde
  作者：J.A. López-Sastre、J.D. Martı́n-Ramos、J.F. Rodrı́guez-Amo、M. Santos-Garcı́a、M.A. Sanz-Tejedor

  DOI：10.1016/s0957-4166(00)00453-5

  日期：2000.12

  The reaction of racemic 3-methylisoxazolines and enantiomerically pure (R-S)- and (S-S)-methanesulfinates and (R-S)- and (S-S)-ethanesulfmates of 1,2:5,6-di-O-isopropylidene-D-glucofuranose allows enantiomerically pure 3-alkylsulfinylmethylisoxazolines with both absolute configurations at sulfur to be obtained. One of these has been used as a chiral nucleophile in the four carbon homologation of 2,3-O-isopropylidene-D-glyceraldehyde 17. (C) 2001 Elsevier Science Ltd. All rights reserved.