(3R,4R,5R)-5,6-O-isopropylidenehex-1-ene-3,4-diol | 106948-25-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3R,4R,5R)-5,6-O-isopropylidenehex-1-ene-3,4-diol
• 英文别名: (1R,2R)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]but-3-ene-1,2-diol
• CAS: 106948-25-8；133321-86-5
• 化学式: C₉H₁₆O₄
• 分子量: 188.224
• InChiKey: HTKCHYLLFFSSIC-BWZBUEFSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3R,4R,5R)-5,6-O-isopropylidenehex-1-ene-3,4-diol 在 二甲基硫 、 臭氧 作用下， 生成 (2S,3R)-3-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,3-dihydroxy-propionaldehyde
  参考文献：
  名称：

  酒石酸二异丙酯改性的（E）-γ-[（环己氧基）二甲基甲硅烷基]-和（E）-γ-（二甲基苯基甲硅烷基）烯丙基硼酸酯：手性试剂，用于对映和非对映选择性合成抗1,2-二醇和2-丁烯-1 ，4-二醇通过醛的α-和γ-羟基形式化

  摘要：

  描述了4-取代的（E）-2-丁烯-1,4-二醇和抗1,2-二醇的对映选择性合成。醛与手性PhMe 2 Si-和（C 6 H 11 O）Me 2 Si-取代的烯丙基硼酸酯25和26的高度非对映选择性反应分别提供反均聚物29和50。29用二甲基二环氧乙烷环氧化，然后经酸催化的中间体环氧硅烷醇进行Petersen重排，可得到具有优异对映选择性（81-87％ee）的1,4-丁二醇27。Tamao氧化50提供抗二醇22（ee的64–72％）。这些程序尤其在与一系列氧化的手性醛进行双不对称反应时获得了优异的结果（图1和2）。这些方法有望用于非环状前体糖的非对映选择性合成中。

  DOI：

  10.1016/s0040-4020(01)88869-4
• 作为产物：
  描述：

  双丙酮-D-甘露糖醇 在 甲醇 、 aluminum (III) chloride 、 sodium periodate 、 lithium aluminium tetrahydride 、 Hoveyda-Grubbs catalyst second generation 、 偶氮二甲酸二异丙酯 、 (S,S)-[CuCl(C₁₀H₆N₃(phenyl)2C₆H₂(CH₃)2C(CH₃)3)] 、 双氧水 、 碳酸氢钠 、 potassium carbonate 、 三苯基膦 、 sodium hydroxide 、 sodium t-butanolate 、 苯酚 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 异丙醇 、 甲苯 为溶剂， 反应 36.5h， 生成 (3R,4R,5R)-5,6-O-isopropylidenehex-1-ene-3,4-diol
  参考文献：
  名称：

  迭代不对称烯丙基取代：通过催化剂控制的顺式和反式1,2-二醇

  摘要：

  铜催化的不对称烯丙基硼化（AAB）使人们可以合成顺式和反式1,2-二醇。该方法便于迭代策略多元醇（参见方案），如完全分化的制备大号-ribo-四醇和保护d -arabino-四醇。P =保护基

  DOI：

  10.1002/anie.201107874

文献信息

• Diisopropyl tartrate modified (E)-γ-[(cyclohexyloxy)dimethylsilyl-allylboronate, a chiral reagent for the stereoselective synthesis of anti 1,2-diols via the formal α-hydroxyallylation of aldehydes
  作者：William R. Roush、Paul T. Gover、Xiaofa Lin

  DOI：10.1016/s0040-4039(00)97299-x

  日期：1990.1

  An enantioselective synthesis of anti 1,2-diols via the reactions of aldehydes and the tartrate ester modified γ(alkoxysilyl)allylboronate2 has been developed. This method is most effective in double asymmetric reactions with chiral aldehydes.

  已经开发了通过醛与酒石酸酯改性的γ（烷氧基甲硅烷基）烯丙基硼酸酯2的反应，对映选择性合成抗1，2-二醇的方法。该方法在与手性醛的双重不对称反应中最有效。
• Reaction of γ,γ-Dialkoxyallylic Zirconium Species with Aldehyde as Protected Acryloyl Anion
  作者：Azusa Sato、Hisanaka Ito、Takeo Taguchi

  DOI：10.1021/jo991107b

  日期：2000.2.1
• 4,5-Diisopropyl-<i>B</i>-[(<i>E</i>)-[(3‘-menthofuryl)dimethylsilyl]allyl]-1,3,2- dioxaborolane, an Improved Chiral Reagent for the Anti α-Hydroxyallylation of Aldehydes:  Application to the Enantioselective Synthesis of (−)-Swainsonine
  作者：J. A. Hunt、William R. Roush

  DOI：10.1021/jo961840s

  日期：1997.2.1

  Diisopropyl tartrate-modified (E)-[gamma-(furyldimethylsilyl)allyl]boronates 10 and 11 were designed for the enantioselective synthesis of substituted anti-3,4-dihydroxy-1-butenes 9 via the anti-alpha-hydroxyallylation of aldehydes. The reactions of aldehydes with 10 and 11 provided furyldimethylsilyl-substituted anti-1,2-silanols 12 and 13 with good enantioselectivity (74-82% ee), and the silanols were oxidized to the corresponding anti-1,2-diols 9 by a modified Fleming-Tamao oxidation protocol. The high reactivity of the (menthofuryl)silane unit toward electrophilic substitution allowed complete protodesilylation of menthofuryl-substituted silanols 13 and subsequent oxidation to diols 9 in a one-pot operation without competing protodesilylation of the allylsilane unit. However, a two-step protocol was required for the protodesilylation-oxidation of the less reactive 2-(5-methyl)-asymmetric reactions with three chiral aldehydes 23-35 (80 to >92% de, with the exception of the mismatched reactions with aldehyde 25, which were essentially unselective). However, [[[2-(5-methylfuryl)]dimethylsilyl]ally]boronate 10 could only be synthesized in less than or equal to 15% yield, and oxidations of the 2-(5-methylfuryl)-substituted silanols 12 were lower-yielding than oxidations of the corresponding menthofuryl-substituted silanols 13. Thus diisopropyl tartrate-modified (E)-[gamma-[(menthofuryl)dimethylsilyl]ally]boronate 11 proved to be the more useful of the two reagents. As a demonstration of the utility of 11 in the synthesis of polyhydroxylated natural products, this new reagent was used in a brief and highly stereoselective synthesis of the naturally occurring alkaloid (-)-swainsonine (42).
• Diisopropyl tartrate-modified (E)-γ-[(menthofuryl)dimethylsilyl]-allyl boronate, an improved chiral reagent for the anti α-hydroxyallylation of aldehydes. Application to the enantioselective synthesis of (−)-swainsonine
  作者：J.A. Hunt、William R. Roush

  DOI：10.1016/0040-4039(94)02295-m

  日期：1995.1

  An enantioselective synthesis of anti 1,2-diols via the reactions of aldehydes and the tartrate ester-modified (E)-gamma-(menthofurylsilyl)allylboronate 5 has been developed. This methodology is applied to a brief, enantioselective synthesis of (-)-swainsonine.