(2R,3S)-3-(tert-Butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-piperidine-1-carboxylic acid tert-butyl ester | 216753-16-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (2R,3S)-3-(tert-Butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-piperidine-1-carboxylic acid tert-butyl ester
• 英文别名: tert-butyl (2R,3S)-3-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]piperidine-1-carboxylate
• CAS: 216753-16-1
• 化学式: C₂₃H₄₉NO₄Si₂
• 分子量: 459.817
• InChiKey: PWSQTDGCHPNMMT-MOPGFXCFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  48
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,3S)-3-(tert-Butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-piperidine-1-carboxylic acid tert-butyl ester 在 正丁基锂 、 四甲基乙二胺 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成
  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：

  [(1R,2S)-2-(tert-Butyl-dimethyl-silanyloxy)-1-(tert-butyl-dimethyl-silanyloxymethyl)-but-3-enyl]-carbamic acid tert-butyl ester 在 Rh on carbon acetylacetonatodicarbonylrhodium(l) 、 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) 作用下， 以 四氢呋喃 、 甲醇 、 乙酸乙酯 为溶剂， 25.0~65.0 ℃ 、202.65 kPa 条件下， 反应 18.0h， 生成 (2R,3S)-3-(tert-Butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-piperidine-1-carboxylic 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

文献信息

• A versatile synthesis of (+)-deoxoprosopinine and (−)-deoxoprosophylline
  作者：Enzo B. Arévalo-García、Juan Carlos Colmenares

  DOI：10.1016/j.tetlet.2008.09.093

  日期：2008.12

  An efficient synthesis of(+)-deoxoprosopinine and (-)-deoxoprosophylline was achieved from N-benzyl-N-Boc serine derivatives (7) and (7). (C) 2008 Elsevier Ltd. All rights reserved.
• [EN] METHOD FOR PREPARATION OF (2R, 3S)-2-(BENZO[D]IMIDAZOLYLPROPYL)PIPERIDIN-3-OL DERIVATIVES<br/>[FR] PROCÉDÉ DE PRÉPARATION DE DÉRIVÉS DE (2R,3S)-2-(BENZO[D]IMIDAZOLYLPROPYL)PIPÉRIDIN-3-OL<br/>[KO] (2R, 3S)-2-(벤조[D]이미다졸일프로필)피페리딘-3-올 유도체의 제조 방법
  申请人：[en]DAEWOONG PHARMACEUTICAL CO., LTD.;[ko]주식회사 대웅제약

  公开号：WO2023113534A1

  公开（公告）日：2023-06-22

  본 발명은 (2R, 3S)-2-(벤조[d]이미다졸일프로필)피페리딘-3-올 유도체의 제조 방법에 관한 것으로, 본 발명에 따른 제조 방법은, 단축된 공정으로도 상기 화합물을 높은 수율로 제조할 수 있다는 이점이 있다.
• Rhodium-Catalyzed Cyclohydrocarbonylation:  Application to the Synthesis of (+)-Prosopinine and (−)-Deoxoprosophylline
  作者：Iwao Ojima、Ephraim S. Vidal

  DOI：10.1021/jo9815608

  日期：1998.10.1

  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.