1,2:5,6-Di-O-isopropylidene-α-D-glucofuranosyl (+)-(R)-2-propanesulfinate | 144712-63-0

• 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-α-D-glucofuranosyl (+)-(R)-2-propanesulfinate
• 英文别名: 1,2:5,6-di-O-isopropylidene-α-D-glucofuranosyl (R)-2-propanesulfinate；S_S-diacetone-D-glucosyl 2-propanesulfinate；[(3aR,5R,6S,6aR)-5-[(4R)-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)-propane-2-sulfinate
• CAS: 144712-63-0
• 化学式: C₁₅H₂₆O₇S
• 分子量: 350.433
• InChiKey: ZRPNHEIDPPDZKZ-YSJJFFLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  23
• 可旋转键数：
  4
• 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-α-D-glucofuranosyl (+)-(R)-2-propanesulfinate 、 对甲苯基溴化镁 以 甲苯 为溶剂， 反应 1.0h， 以89%的产率得到(S)-isopropyl p-tolyl sulfoxide
  参考文献：
  名称：

  Asymmetric synthesis of alkane- and arenesulfinates of diacetone-D-glucose (DAG): an improved and general route to both enantiomerically pure sulfoxides

  摘要：

  Diacetone-D-glucose (DAG), a commercially available, sugar-derived secondary alcohol, was found to react with alkane- and arenesulfinyl chlorides in the presence of a tertiary amine in a very useful manner. When i-Pr2Net is used as the base, (-)-(S)-alkane- and arenesulfinates are obtained in 50-90% yield with 89-greater-than-or-equal-to 95% de. Simply changing the base from i-Pr2NEt to Py affords (+)-(R)-alkane- and arenesulfinates in 56-87% yield with 70-greater-than-or-equal-to 95% de. The de's were determined by H-1 NMR. Optically pure alkane- and arenesulfinates are obtained either by recrystallization or by column chromatography. These sulfinates were transformed into various enantiomerically pure sulfoxides (alkyl alkyl and alkyl aryl) by reaction with different Grignard reagents. This new methodology is cheap, quick, and very convenient when both enantiomers of a given sulfoxide are needed enantiomerically pure. The influence of the solvent, as well as the effect of other types of bases, on the stereochemical course of the reaction has been evaluated, and a possible origin of the diastereoselectivity is discussed. Other optically pure secondary alcohols are used m the same reaction, and the comparison of their behavior with that of DAG is also reported.

  DOI：

  10.1021/jo00051a022
• 作为产物：
  描述：

  isopropylsulfinyl chloride 、 双丙酮葡萄糖 在 吡啶 作用下， 以 四氢呋喃 为溶剂， 以56%的产率得到1,2:5,6-Di-O-isopropylidene-α-D-glucofuranosyl (+)-(R)-2-propanesulfinate
  参考文献：
  名称：

  Asymmetric synthesis of alkane- and arenesulfinates of diacetone-D-glucose (DAG): an improved and general route to both enantiomerically pure sulfoxides

  摘要：

  Diacetone-D-glucose (DAG), a commercially available, sugar-derived secondary alcohol, was found to react with alkane- and arenesulfinyl chlorides in the presence of a tertiary amine in a very useful manner. When i-Pr2Net is used as the base, (-)-(S)-alkane- and arenesulfinates are obtained in 50-90% yield with 89-greater-than-or-equal-to 95% de. Simply changing the base from i-Pr2NEt to Py affords (+)-(R)-alkane- and arenesulfinates in 56-87% yield with 70-greater-than-or-equal-to 95% de. The de's were determined by H-1 NMR. Optically pure alkane- and arenesulfinates are obtained either by recrystallization or by column chromatography. These sulfinates were transformed into various enantiomerically pure sulfoxides (alkyl alkyl and alkyl aryl) by reaction with different Grignard reagents. This new methodology is cheap, quick, and very convenient when both enantiomers of a given sulfoxide are needed enantiomerically pure. The influence of the solvent, as well as the effect of other types of bases, on the stereochemical course of the reaction has been evaluated, and a possible origin of the diastereoselectivity is discussed. Other optically pure secondary alcohols are used m the same reaction, and the comparison of their behavior with that of DAG is also reported.

  DOI：

  10.1021/jo00051a022

文献信息

• Studies on chemo- and diastereo-selectivity of the Diels–Alder reactions of sulfinyltoluquinones with cyclopentadiene
  作者：Andrea L. F. de Sousa、José E. P. Cardoso Filho、Blanka Wladislaw、Liliana Marzorati、Claudio Di Vitta

  DOI：10.1139/v09-070

  日期：2009.8

  Sulfinyltoluquinones (2a–2c) were submitted to thermal or catalyzed [4+2] cycloaddition reactions with cyclopentadiene. For p-tolylsulfinyltoluquinones (2b) and (2c), almost complete C2–C3-chemo- and unlike-diastereoselectivity was achieved by catalysis with ZnBr₂, yielding adducts 6. Under thermal conditions, Diels–Alder reaction took place at the C5–C6 double bonds of quinones 2a–2c, generating mixtures of diastereoisomeric like- and unlike-adducts 4.

  亚磺酰基甲苯醌（2a-2c）与环戊二烯进行了热反应或催化 [4+2] 环加成反应。对于对甲苯磺酰基甲苯醌 (2b) 和 (2c)，在 ZnBr2 催化下几乎完全实现了 C2-C3 化学选择性和非双向选择性，生成了加合物 6。在热条件下，醌类化合物 2a-2c 的 C5-C6 双键发生了 Diels-Alder 反应，生成了非对映异构的同类和异类加合物混合物 4。
• An improved and efficient procedure for the preparation of chiral sulfinates from sulfonyl chloride using triphenylphosphine
  作者：Yoshihiko Watanabe、Nobuyuki Mase、Moto-aki Tateyama、Takeshi Toru

  DOI：10.1016/s0957-4166(99)00066-x

  日期：1999.2

  An improved procedure of the Sharpless method for the preparation of chiral sulfinates by triphenylphosphine is described. A mixture of sulfonyl chlorides and diacetone-d-glucose or l-menthol in the presence of triethylamine was treated with triphenylphosphine in CH2Cl2 at 0°C to give the sulfinates in good yields.

  描述了通过三苯基膦制备手性亚磺酸盐的Sharpless方法的改进方法。在三乙胺存在下，将磺酰氯和双丙酮-d-葡萄糖或1-薄荷醇的混合物在0℃下在CH 2 Cl 2中用三苯基膦处理，以良好的产率得到亚磺酸盐。
• Alcudia, Felipe; Fernandez, Inmaculada; Khiar, Noureddine, Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 74, # 1-4, p. 393 - 394
  作者：Alcudia, Felipe、Fernandez, Inmaculada、Khiar, Noureddine、Llera, Jose Manuel

  DOI：——

  日期：——