trans-2-(1-methylethenyl)-7-(phenylmethoxy)-3,6,7-trimethyl-4-octenal | 142700-42-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-2-(1-methylethenyl)-7-(phenylmethoxy)-3,6,7-trimethyl-4-octenal
• 英文别名: (E,2R,3R,6S)-3,6,7-trimethyl-7-phenylmethoxy-2-prop-1-en-2-yloct-4-enal
• CAS: 142700-42-3
• 化学式: C₂₁H₃₀O₂
• 分子量: 314.468
• InChiKey: JFNGNIVMKZWMFD-JLSRHLEQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-2-(1-methylethenyl)-7-(phenylmethoxy)-3,6,7-trimethyl-4-octenal 在 potassium fluoride 、 正丁基锂 、 四甲基乙二胺 、 仲丁基锂 、 lithium 作用下， 以 甲醇 、 甲苯 、 甲胺 为溶剂， 反应 18.8h， 生成 6-methyl-7-(5-hydroxy-1,4,5-trimethyl-2-hexenyl)-2,3,3a,6,7,7a-hexahydroindan-4(5H)-one
  参考文献：
  名称：

  An intramolecular Diels-Alder approach to the cis ring fused isomer of the 25-hydroxy vitamin D2 Grundmann ketone

  摘要：

  Stereospecific Claisen and intramolecular Diels-Alder reactions of chiral ester synthon 4 results in conversion of a single asymmetric center of commercially available ester 4 to a vitamin D synthon, the C/D cis Grundmann ketone 3. The addition of propenyllithium to aldehyde 9 was dominated by a chelated anti-Cram transition state and yielded the threo isomer 12a as the major product. The stereochemistry of 12a was determined by X-ray crystallography. Conversion of benzyl-protected erythro isomer 11b to its dimethylacryloyl ester followed by ester enolate Claisen rearrangement led to the C17 and C20 stereochemistry of vitamin D. Addition of a pentadienyl anion to aldehyde 15 gave a tetraene, 17, which underwent an intramolecular Diels-Alder reaction to produce compound 18. Removal of the C16 hydroxyl and hydrolysis gave only the cis-fused isomer of 3.

  DOI：

  10.1021/jo00042a014
• 作为产物：
  描述：

  (2S)-2,3-二甲基-1,3-丁二醇 在 盐酸 、 lithium aluminium tetrahydride 、 正丁基锂 、 三甲基氯硅烷 、 草酰氯 、 2,2,6,6-tetramethylpiperidinyl-lithium 、 lithium 、 sodium hydride 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 反应 6.67h， 生成 trans-2-(1-methylethenyl)-7-(phenylmethoxy)-3,6,7-trimethyl-4-octenal
  参考文献：
  名称：

  An intramolecular Diels-Alder approach to the cis ring fused isomer of the 25-hydroxy vitamin D2 Grundmann ketone

  摘要：

  Stereospecific Claisen and intramolecular Diels-Alder reactions of chiral ester synthon 4 results in conversion of a single asymmetric center of commercially available ester 4 to a vitamin D synthon, the C/D cis Grundmann ketone 3. The addition of propenyllithium to aldehyde 9 was dominated by a chelated anti-Cram transition state and yielded the threo isomer 12a as the major product. The stereochemistry of 12a was determined by X-ray crystallography. Conversion of benzyl-protected erythro isomer 11b to its dimethylacryloyl ester followed by ester enolate Claisen rearrangement led to the C17 and C20 stereochemistry of vitamin D. Addition of a pentadienyl anion to aldehyde 15 gave a tetraene, 17, which underwent an intramolecular Diels-Alder reaction to produce compound 18. Removal of the C16 hydroxyl and hydrolysis gave only the cis-fused isomer of 3.

  DOI：

  10.1021/jo00042a014

文献信息

• An intramolecular Diels-Alder approach to the cis ring fused isomer of the 25-hydroxy vitamin D2 Grundmann ketone
  作者：Stephen R. Wilson、Linda Jacob

  DOI：10.1021/jo00042a014

  日期：1992.7

  Stereospecific Claisen and intramolecular Diels-Alder reactions of chiral ester synthon 4 results in conversion of a single asymmetric center of commercially available ester 4 to a vitamin D synthon, the C/D cis Grundmann ketone 3. The addition of propenyllithium to aldehyde 9 was dominated by a chelated anti-Cram transition state and yielded the threo isomer 12a as the major product. The stereochemistry of 12a was determined by X-ray crystallography. Conversion of benzyl-protected erythro isomer 11b to its dimethylacryloyl ester followed by ester enolate Claisen rearrangement led to the C17 and C20 stereochemistry of vitamin D. Addition of a pentadienyl anion to aldehyde 15 gave a tetraene, 17, which underwent an intramolecular Diels-Alder reaction to produce compound 18. Removal of the C16 hydroxyl and hydrolysis gave only the cis-fused isomer of 3.