(3R,4S,5R)-6-<(tert-butyldimethylsilyl)oxy>-3-<<2'-(4',5',6',7'-tetrahydro-3',6'-dimethylbenzofuryl)>dimethylsilyl>-5-methylhex-1-en-4-ol | 185953-43-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (3R,4S,5R)-6-<(tert-butyldimethylsilyl)oxy>-3-<<2'-(4',5',6',7'-tetrahydro-3',6'-dimethylbenzofuryl)>dimethylsilyl>-5-methylhex-1-en-4-ol
• 英文别名: (2R,3S,4R)-1-[tert-butyl(dimethyl)silyl]oxy-4-[(3,6-dimethyl-4,5,6,7-tetrahydro-1-benzofuran-2-yl)-dimethylsilyl]-2-methylhex-5-en-3-ol
• CAS: 185953-43-9
• 化学式: C₂₅H₄₆O₃Si₂
• 分子量: 450.809
• InChiKey: WLQADXVRDDTLIF-JPDJHPSGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  42.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R,4S,5R)-6-<(tert-butyldimethylsilyl)oxy>-3-<<2'-(4',5',6',7'-tetrahydro-3',6'-dimethylbenzofuryl)>dimethylsilyl>-5-methylhex-1-en-4-ol 在 potassium fluoride 、 双氧水 、 potassium hydrogencarbonate 、 三氟乙酸 作用下， 生成 (3R,4S,5R)-6-<(tert-butyldimethylsilyl)oxy>-5-methylhex-1-ene-3,4-diol
  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：

  (2R)-3-(tert-butyldimethylsilyloxy)-2-methylpropanal 、 dipropan-2-yl (4S,5S)-2-[(E)-3-[(3,6-dimethyl-4,5,6,7-tetrahydro-1-benzofuran-2-yl)-dimethylsilyl]prop-2-enyl]-1,3,2-dioxaborolane-4,5-dicarboxylate 在 4 Angstroem MS 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以7%的产率得到(3S,4R,5R)-6-<(tert-butyldimethylsilyl)oxy>-3-<<2'-(4',5',6',7'-tetrahydro-3',6'-dimethylbenzofuryl)>dimethylsilyl>-5-methylhex-1-en-4-ol
  参考文献：
  名称：

  4,5-Diisopropyl-B-[(E)-[(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

  摘要：

  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).

  DOI：

  10.1021/jo961840s