(+)-xylo-(4R,5S,6S)-hept-1-ene-4,5,6,7-tetrol | 131484-31-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (+)-xylo-(4R,5S,6S)-hept-1-ene-4,5,6,7-tetrol
• 英文别名: 5,6,7-trideoxy-D-xylo-hept-6-enitol；(2S,3S,4R)-hept-6-ene-1,2,3,4-tetrol
• CAS: 131484-31-6
• 化学式: C₇H₁₄O₄
• 分子量: 162.186
• InChiKey: UGFVKDFCBKARNH-VQVTYTSYSA-N

物化性质

• 沸点：
  374.4±42.0 °C(Predicted)
• 密度：
  1.244±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  80.9
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+)-xylo-(4R,5S,6S)-hept-1-ene-4,5,6,7-tetrol 在 臭氧 、 sodium sulfite 作用下， 生成 2-deoxy-L-gulose
  参考文献：
  名称：

  Substrate specificity and carbohydrate synthesis using transketolase

  摘要：

  This paper describes the use of the enzyme transketolase as a catalyst in organic synthesis. The properties of transketolase from both yeast and spinach were investigated. The yeast enzyme was found to be more convenient for routine use. Examination of the substrate specificity of yeast transketolase demonstrated that the enzyme accepts a wide variety of 2-hydroxy aldehydes as substrates. A practical protocol for transketolase-catalyzed condensation of hydroxypyruvic acid with these aldehydes has been developed and used for the synthesis of four carbohydrates: L-idose, L-gulose, 2-deoxy-L-xylohexose, and L-xylose.

  DOI：

  10.1021/jo00048a023
• 作为产物：
  描述：

  (+)-ribo-(4R,5R,6S)-7-(tert-butyldiphenylsiloxy)-5,6-epoxyhept-1-en-4-ol 在 吡啶 、 硫酸 、 四丁基氟化铵 、 sodium methylate 、 氯化二乙基铝 作用下， 以 二氯甲烷 为溶剂， 生成 (+)-xylo-(4R,5S,6S)-hept-1-ene-4,5,6,7-tetrol
  参考文献：
  名称：

  A stereochemically general synthesis of 2-deoxyhexoses via the asymmetric allylboration of 2,3-epoxy aldehydes

  摘要：

  A stereochemically general strategy for the synthesis of 2-deoxyhexoses is described. This new approach involves the asymmetric allylboration of epoxy aldehydes 12 and 13, prepared via the Sharpless asymmetric epoxidation reaction, as a means of establishing the stereochemistry of the sugar backbone. Thus, the matched double asymmetric allylborations of 12 and 13 using tartrate allylboronates (R,R)- and (S,S)-7, respectively, provide erythro epoxy alcohols 14 and 16 with excellent diastereoselectivity ( > 96:4) and enantioselectivity (greater-than-or-equal-to 96% ee). The mismatched double asymmetric reactions of 12 and 13 using (S,S)- and (R,R)-7, respectively, provided the diastereomeric threo epoxy alcohols 15 and 17 with lower (ca. 75:25) but still synthetically useful selectivity. The enantiomeric purity of the major diastereomer in each of these reactions was determined to be greater than that of the epoxy aldehyde precursors. Epoxy alcohols 14 and 16 were converted with excellent selectivity to the l-arabino (21) and l-xylo (26) tetrols via neighboring group assisted alpha-substitution reactions of the derived phenylurethane derivatives 18 and 23. Stereochemically complementary beta-opening reactions were accomplished by treating primary alcohols 38, 40, 42, and 44 [prepared from 14-17, respectively, by ethoxyethylation of C(4)-OH and removal of the C(7)-tert-butyldiphenylsilyl (TBDPS) ethers] with NaOH in aqueous t-BuOH at reflux. Acid-catalyzed hydrolysis of the C(4)-ethoxyethyl ethers then provided tetrols d-35 (from 14), d-21 (from 15), d-30 (from 16), and d-26 (from 17), each with excellent stereoselectivity. These tetrols were isolated and fully characterized as the tetraacetate derivatives 36, 22, 31, and 27, respectively. These beta-opening reactions proceed by way of an epoxide migration (29 to 33) that inverts the stereochemistry at C(6) and activates C(7) toward nucleophilic attack. It is necessary that the C(4) hydroxyl be protected in three of the four stereoisomeric series to minimize competitive epoxide migration pathways (cf. 29 to 32a). arabino tetrol 21 and lyxo tetrol 30 were converted to 2-deoxyglucose and 2-deoxygalactose, respectively, by a standard ozonolytic sequence and then to 2-deoxyglucitol pentaacetate (45) and 2-deoxygalactitol pentaacetate (46) via NaBH4 reduction of the 2-deoxy sugars, thereby confirming all stereochemical assignments. The epoxide beta-opening technology was also applied to epoxy benzyl ether 47 (prepared from 14) and epoxy BOM ether 49 (deriving from 16). These reactions provide tetrol derivatives 48 and 50, respectively, in which the C(4)- and C(5)-hydroxyl functionality are suitably differentiated for use in subsequent synthetic sequences.

  DOI：

  10.1021/jo00004a053

文献信息

• Schimid, Walther; Whitesides, George M., Journal of the American Chemical Society, 1991, vol. 113, # 17, p. 6674 - 6675
  作者：Schimid, Walther、Whitesides, George M.

  DOI：——

  日期：——
• A stereochemically general synthesis of 2-deoxyhexoses via the asymmetric allylboration of 2,3-epoxy aldehydes
  作者：William R. Roush、Julie A. Straub、Michael S. VanNieuwenhze

  DOI：10.1021/jo00004a053

  日期：1991.2

  A stereochemically general strategy for the synthesis of 2-deoxyhexoses is described. This new approach involves the asymmetric allylboration of epoxy aldehydes 12 and 13, prepared via the Sharpless asymmetric epoxidation reaction, as a means of establishing the stereochemistry of the sugar backbone. Thus, the matched double asymmetric allylborations of 12 and 13 using tartrate allylboronates (R,R)- and (S,S)-7, respectively, provide erythro epoxy alcohols 14 and 16 with excellent diastereoselectivity ( > 96:4) and enantioselectivity (greater-than-or-equal-to 96% ee). The mismatched double asymmetric reactions of 12 and 13 using (S,S)- and (R,R)-7, respectively, provided the diastereomeric threo epoxy alcohols 15 and 17 with lower (ca. 75:25) but still synthetically useful selectivity. The enantiomeric purity of the major diastereomer in each of these reactions was determined to be greater than that of the epoxy aldehyde precursors. Epoxy alcohols 14 and 16 were converted with excellent selectivity to the l-arabino (21) and l-xylo (26) tetrols via neighboring group assisted alpha-substitution reactions of the derived phenylurethane derivatives 18 and 23. Stereochemically complementary beta-opening reactions were accomplished by treating primary alcohols 38, 40, 42, and 44 [prepared from 14-17, respectively, by ethoxyethylation of C(4)-OH and removal of the C(7)-tert-butyldiphenylsilyl (TBDPS) ethers] with NaOH in aqueous t-BuOH at reflux. Acid-catalyzed hydrolysis of the C(4)-ethoxyethyl ethers then provided tetrols d-35 (from 14), d-21 (from 15), d-30 (from 16), and d-26 (from 17), each with excellent stereoselectivity. These tetrols were isolated and fully characterized as the tetraacetate derivatives 36, 22, 31, and 27, respectively. These beta-opening reactions proceed by way of an epoxide migration (29 to 33) that inverts the stereochemistry at C(6) and activates C(7) toward nucleophilic attack. It is necessary that the C(4) hydroxyl be protected in three of the four stereoisomeric series to minimize competitive epoxide migration pathways (cf. 29 to 32a). arabino tetrol 21 and lyxo tetrol 30 were converted to 2-deoxyglucose and 2-deoxygalactose, respectively, by a standard ozonolytic sequence and then to 2-deoxyglucitol pentaacetate (45) and 2-deoxygalactitol pentaacetate (46) via NaBH4 reduction of the 2-deoxy sugars, thereby confirming all stereochemical assignments. The epoxide beta-opening technology was also applied to epoxy benzyl ether 47 (prepared from 14) and epoxy BOM ether 49 (deriving from 16). These reactions provide tetrol derivatives 48 and 50, respectively, in which the C(4)- and C(5)-hydroxyl functionality are suitably differentiated for use in subsequent synthetic sequences.
• Substrate specificity and carbohydrate synthesis using transketolase
  作者：Yoshihiro Kobori、David C. Myles、George M. Whitesides

  DOI：10.1021/jo00048a023

  日期：1992.10

  This paper describes the use of the enzyme transketolase as a catalyst in organic synthesis. The properties of transketolase from both yeast and spinach were investigated. The yeast enzyme was found to be more convenient for routine use. Examination of the substrate specificity of yeast transketolase demonstrated that the enzyme accepts a wide variety of 2-hydroxy aldehydes as substrates. A practical protocol for transketolase-catalyzed condensation of hydroxypyruvic acid with these aldehydes has been developed and used for the synthesis of four carbohydrates: L-idose, L-gulose, 2-deoxy-L-xylohexose, and L-xylose.