(2S,3R)-6-bromo-2,3-epoxyhexanal | 185953-53-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: (2S,3R)-6-bromo-2,3-epoxyhexanal
• 英文别名: (2S,3R)-3-(3-bromopropyl)oxirane-2-carbaldehyde
• CAS: 185953-53-1
• 化学式: C₆H₉BrO₂
• 分子量: 193.04
• InChiKey: FRJWMMVUHUPPAN-PHDIDXHHSA-N

物化性质

• 沸点：
  248.7±15.0 °C(Predicted)
• 密度：
  1.634±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  29.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3R)-6-bromo-2,3-epoxyhexanal 在 盐酸 、 potassium fluoride 、 3 A molecular sieve 、 4 A molecular sieve 、 ammonium acetate 、 双氧水 、 4-甲基苯磺酸吡啶 、 sodium cyanoborohydride 、 potassium hydrogencarbonate 、 臭氧 、 三苯基膦 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 2.0h， 生成 八倾吲嗪三醇
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/0040-4039(94)02295-m
• 作为产物：
  描述：

  (E)-6-bromohex-2-en-1-ol 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 pyridine-SO3 complex 、 4 A molecular sieve 、 D-(-)-酒石酸二异丙酯 、 二甲基亚砜 、 三乙胺 作用下， 生成 (2S,3R)-6-bromo-2,3-epoxyhexanal
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/0040-4039(94)02295-m

文献信息

• 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.