((1S,2R)-2-Triisopropylsilanyloxy-1-triisopropylsilanyloxymethyl-but-3-enyl)-carbamic acid tert-butyl ester | 216753-17-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: ((1S,2R)-2-Triisopropylsilanyloxy-1-triisopropylsilanyloxymethyl-but-3-enyl)-carbamic acid tert-butyl ester
• 英文别名: tert-butyl N-[(2S,3R)-1,3-bis[tri(propan-2-yl)silyloxy]pent-4-en-2-yl]carbamate
• CAS: 216753-17-2
• 化学式: C₂₈H₅₉NO₄Si₂
• 分子量: 529.952
• InChiKey: UTJMGSQNWMJWCR-IZZNHLLZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.82
• 重原子数：
  35
• 可旋转键数：
  16
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  56.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ((1S,2R)-2-Triisopropylsilanyloxy-1-triisopropylsilanyloxymethyl-but-3-enyl)-carbamic acid tert-butyl ester 在 palladium on activated charcoal acetylacetonatodicarbonylrhodium(l) 、 三氟化硼乙醚 、 四丁基氟化铵 、 氢气 、 6,6′-[(3,3′-二叔丁基-5,5′-二甲氧基-1,1′-二苯基-2,2′-二基)双(氧)]双(二苯并[d,f][1,3,2]二噁磷杂庚英) 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， -78.0~65.0 ℃ 、405.3 kPa 条件下， 反应 25.0h， 生成 desoxoprosophylline
  参考文献：
  名称：

  Rhodium-Catalyzed Cyclohydrocarbonylation:  Application to the Synthesis of (+)-Prosopinine and (−)-Deoxoprosophylline

  摘要：

  Efficient convergent total syntheses of (+)-prosopinine (1) and (-)-deoxoprosophylline (4) were accomplished using Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation as the key step. The Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation of I, derived from (R)-serine, at 65 degrees C and 4 atm of CO and H-2 (1:1) in ethanol afforded 6-ethoxypiperidine II, which was transformed to enantiopure (+)-prosopinine (1) in 3 steps. In a similar manner, (-)-deoxoprosophylline was synthesized through cyclohydrocarbonylation of IV derived from (S)-serine, giving 6-ethoxypiperidine V. The key intermediate V was transformed to enantiopure (-)-deoxoprosophylline (4) in 4 steps. These two short total syntheses clearly demonstrate the usefulness of the extremely regioselective cyclohydrocarbonylation process developed in these laboratories for the concise syntheses of piperidine alkaloids and related compounds.

  DOI：

  10.1021/jo9815608
• 作为产物：
  描述：

  三异丙基氯硅烷 、 tert-butyl ((2S,3R)-1,3-dihydroxypent-4-en-2-yl)carbamate 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以72%的产率得到((1S,2R)-2-Triisopropylsilanyloxy-1-triisopropylsilanyloxymethyl-but-3-enyl)-carbamic acid tert-butyl ester
  参考文献：
  名称：

  Rhodium-Catalyzed Cyclohydrocarbonylation:  Application to the Synthesis of (+)-Prosopinine and (−)-Deoxoprosophylline

  摘要：

  Efficient convergent total syntheses of (+)-prosopinine (1) and (-)-deoxoprosophylline (4) were accomplished using Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation as the key step. The Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation of I, derived from (R)-serine, at 65 degrees C and 4 atm of CO and H-2 (1:1) in ethanol afforded 6-ethoxypiperidine II, which was transformed to enantiopure (+)-prosopinine (1) in 3 steps. In a similar manner, (-)-deoxoprosophylline was synthesized through cyclohydrocarbonylation of IV derived from (S)-serine, giving 6-ethoxypiperidine V. The key intermediate V was transformed to enantiopure (-)-deoxoprosophylline (4) in 4 steps. These two short total syntheses clearly demonstrate the usefulness of the extremely regioselective cyclohydrocarbonylation process developed in these laboratories for the concise syntheses of piperidine alkaloids and related compounds.

  DOI：

  10.1021/jo9815608