(3R,4S,5R)-5,6-O-isopropylidene-3-<<2'-(4',5',6',7'-tetrahydro-3',6'-dimethylbenzofuryl)>dimethylsilyl>hex-1-en-4-ol | 185953-39-3

• 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)-5,6-O-isopropylidene-3-<<2'-(4',5',6',7'-tetrahydro-3',6'-dimethylbenzofuryl)>dimethylsilyl>hex-1-en-4-ol
• CAS: 185953-39-3
• 化学式: C₂₁H₃₄O₄Si
• 分子量: 378.584
• InChiKey: XZDMYFSYSAHNLO-DWVSEIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  26.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  51.83
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (3R,4S,5R)-5,6-O-isopropylidene-3-<<2'-(4',5',6',7'-tetrahydro-3',6'-dimethylbenzofuryl)>dimethylsilyl>hex-1-en-4-ol 在 potassium fluoride 、 双氧水 、 potassium hydrogencarbonate 、 三氟乙酸 作用下， 生成 (3R,4R,5R)-5,6-O-isopropylidenehex-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：

  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 、 (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 4 A molecular sieve 作用下， 以 甲苯 为溶剂， 以79%的产率得到(3R,4S,5R)-5,6-O-isopropylidene-3-<<2'-(4',5',6',7'-tetrahydro-3',6'-dimethylbenzofuryl)>dimethylsilyl>hex-1-en-4-ol
  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).