(1R,3S,12R,17R)-3-<(tert-butyldimethylsiloxy)methyl>-13,14-didehydro-18-oxoberban | 146309-84-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: (1R,3S,12R,17R)-3-<(tert-butyldimethylsiloxy)methyl>-13,14-didehydro-18-oxoberban
• 英文别名: (1R,3S,12R,17R)-3-[(tert-butyldimethylsiloxy)methyl]-13,14-didehydro-18-oxoberban；(6S,8aR,12aS,13aR)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-5,6,8a,9,10,12a,13,13a-octahydroisoquinolino[2,1-b]isoquinolin-8-one
• CAS: 146309-84-4
• 化学式: C₂₄H₃₅NO₂Si
• 分子量: 397.633
• InChiKey: HFKCQRGMELUIPQ-NPDDRXJXSA-N

物化性质

• 沸点：
  492.0±45.0 °C(predicted)
• 密度：
  1.07±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.49
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,3S,12R,17R)-3-<(tert-butyldimethylsiloxy)methyl>-13,14-didehydro-18-oxoberban 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以77%的产率得到(1R,3S,12R,17R)-3-(hydroxymethyl)-13,14-didehydro-18-oxoberban
  参考文献：
  名称：

  A highly effective one-pot bicycloannulation methodology for the synthesis of berban and yohimban systems based on organotin-mediated three-component coupling (N-acylative pentadienylation of C:N bonds)

  摘要：

  A highly effective bicycloannulation methodology for the synthesis of berban and yohimban alkaloid systems is described. Three-component coupling reactions of 2,4-pentadienyltin reagents with C=N bonds and alpha,beta-unsaturated acyl chlorides furnish bicycloannulated products in a one-pot operation. For example, the reactions of 2,4-pentadienyltributyltin (1) with isoquinoline derivatives activated by acryloyl chloride afford the tetracyclic (+/-)-allo-berban systems stereoselectively. Similarly, the reaction of 1 with 3,4-dihydro-beta-carboline (11) gives the pentacyclic (+/-)-allo-yohimban system. The reaction is not affected by the stereochemistry of the 2,4-pentadienyltin reagent. A new substituted 2,4-pentadienyltin reagent, 3-(hydroxymethyl)-2,4-pentadienyltrimethyltin (19), is prepared via 3-(hydroxymethyl)pentadienyl dianion. The three-component coupling reaction of 19 with 11 and acryloyl chloride affords the (+/-)-allo-16-(hydroxymethyl)yohimban system, from which (+/-)-nitraraine is readily synthesized. In addition, 1,3-asymmetric induction leads to the high diastereoselectivity realized in bicycloannulation (up to 94% de) when (S)-3-[(tert-butyldimethylsiloxy)methyl]-3,4-dihydroisoquinoline (27), which is readily derived from L-phenylalanine, is used in the three-component coupling reaction.

  DOI：

  10.1021/jo00057a028
• 作为产物：
  描述：

  (3S)-3-(tert-butyldimethylsilyloxymethyl)-1,2,3,4-tetrahydroisoquinoline 在 氢氧化钾 、 N-氯代丁二酰亚胺 、 四丁基碘化铵 作用下， 以 二氯甲烷 为溶剂， 反应 50.0h， 生成 (1R,3S,12R,17R)-3-<(tert-butyldimethylsiloxy)methyl>-13,14-didehydro-18-oxoberban
  参考文献：
  名称：

  A highly effective one-pot bicycloannulation methodology for the synthesis of berban and yohimban systems based on organotin-mediated three-component coupling (N-acylative pentadienylation of C:N bonds)

  摘要：

  A highly effective bicycloannulation methodology for the synthesis of berban and yohimban alkaloid systems is described. Three-component coupling reactions of 2,4-pentadienyltin reagents with C=N bonds and alpha,beta-unsaturated acyl chlorides furnish bicycloannulated products in a one-pot operation. For example, the reactions of 2,4-pentadienyltributyltin (1) with isoquinoline derivatives activated by acryloyl chloride afford the tetracyclic (+/-)-allo-berban systems stereoselectively. Similarly, the reaction of 1 with 3,4-dihydro-beta-carboline (11) gives the pentacyclic (+/-)-allo-yohimban system. The reaction is not affected by the stereochemistry of the 2,4-pentadienyltin reagent. A new substituted 2,4-pentadienyltin reagent, 3-(hydroxymethyl)-2,4-pentadienyltrimethyltin (19), is prepared via 3-(hydroxymethyl)pentadienyl dianion. The three-component coupling reaction of 19 with 11 and acryloyl chloride affords the (+/-)-allo-16-(hydroxymethyl)yohimban system, from which (+/-)-nitraraine is readily synthesized. In addition, 1,3-asymmetric induction leads to the high diastereoselectivity realized in bicycloannulation (up to 94% de) when (S)-3-[(tert-butyldimethylsiloxy)methyl]-3,4-dihydroisoquinoline (27), which is readily derived from L-phenylalanine, is used in the three-component coupling reaction.

  DOI：

  10.1021/jo00057a028

文献信息

• A highly effective one-pot bicycloannulation methodology for the synthesis of berban and yohimban systems based on organotin-mediated three-component coupling (N-acylative pentadienylation of C:N bonds)
  作者：Ryohei Yamaguchi、Takashi Hamasaki、Tohru Sasaki、Tetsuo Ohta、Kiitiro Utimoto、Sinpei Kozima、Hidemasa Takaya

  DOI：10.1021/jo00057a028

  日期：1993.2

  A highly effective bicycloannulation methodology for the synthesis of berban and yohimban alkaloid systems is described. Three-component coupling reactions of 2,4-pentadienyltin reagents with C=N bonds and alpha,beta-unsaturated acyl chlorides furnish bicycloannulated products in a one-pot operation. For example, the reactions of 2,4-pentadienyltributyltin (1) with isoquinoline derivatives activated by acryloyl chloride afford the tetracyclic (+/-)-allo-berban systems stereoselectively. Similarly, the reaction of 1 with 3,4-dihydro-beta-carboline (11) gives the pentacyclic (+/-)-allo-yohimban system. The reaction is not affected by the stereochemistry of the 2,4-pentadienyltin reagent. A new substituted 2,4-pentadienyltin reagent, 3-(hydroxymethyl)-2,4-pentadienyltrimethyltin (19), is prepared via 3-(hydroxymethyl)pentadienyl dianion. The three-component coupling reaction of 19 with 11 and acryloyl chloride affords the (+/-)-allo-16-(hydroxymethyl)yohimban system, from which (+/-)-nitraraine is readily synthesized. In addition, 1,3-asymmetric induction leads to the high diastereoselectivity realized in bicycloannulation (up to 94% de) when (S)-3-[(tert-butyldimethylsiloxy)methyl]-3,4-dihydroisoquinoline (27), which is readily derived from L-phenylalanine, is used in the three-component coupling reaction.