(d,l)-2-chloro-7-(1-tert-butyldimethylsiloxy-1-methylethyl)-6,7-dihydro-5H-1-pyrindine | 175228-33-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: (d,l)-2-chloro-7-(1-tert-butyldimethylsiloxy-1-methylethyl)-6,7-dihydro-5H-1-pyrindine
• 英文别名: tert-butyl-[2-(2-chloro-6,7-dihydro-5H-cyclopenta[b]pyridin-7-yl)propan-2-yloxy]-dimethylsilane
• CAS: 175228-33-8
• 化学式: C₁₇H₂₈ClNOSi
• 分子量: 325.954
• InChiKey: PXWYHOODFUIWMQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.57
• 重原子数：
  21.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  22.12
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (d,l)-2-chloro-7-(1-tert-butyldimethylsiloxy-1-methylethyl)-6,7-dihydro-5H-1-pyrindine 在 三苯基膦 、 nickel dichloride 、 锌 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 8.0h， 生成 (7R,7R')-7,7'-di(1-tert-butyldimethylsiloxy-1-methylethyl)-6,6',7,7'-tetrahydro-5H,5H'-2,2'-bi-1,1'-pyrindine
  参考文献：
  名称：

  Enantiopsecific Ring Expansion of Oxetanes: Stereoselective Synthesis of Tetrahydrofurans

  摘要：

  Enantiospecific ring expansion of oxetanes to tetrahydrofurans with diazoacetic acid ester was found to be catalyzed by the copper complex of (7R,7'R)-7,7'-di(1-tert-butyldimethylsiloxy-1-methylethyl)-6,6',7,7'-tetrahydro-5H,5'H-2,2'-bi-1,1'-pyrindine (4). For example, the reaction of (R)-2-phenyloxetane of 89% ee and tert-buryl diazoacetate with Cu-4 complex as a catalyst provided (2S,3R)-tert-butyl 3-phenyltetrahydrofuran-2-carboxylate of 92% ee as a major product, while that of (S)-2-phenyloxetane of 85% ee provided (2S,3S)-tert-butyl 3-phenyltetrahydrofuran-2-carboxylate of 93% ee as a major one.

  DOI：

  10.3987/com-95-s35
• 作为产物：
  描述：

  2-氯-6,7-二氢-5H环戊[b]并吡啶 在 2,6-二甲基吡啶 、 正丁基锂 、 二异丙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.67h， 生成 (d,l)-2-chloro-7-(1-tert-butyldimethylsiloxy-1-methylethyl)-6,7-dihydro-5H-1-pyrindine
  参考文献：
  名称：

  Enantiopsecific Ring Expansion of Oxetanes: Stereoselective Synthesis of Tetrahydrofurans

  摘要：

  Enantiospecific ring expansion of oxetanes to tetrahydrofurans with diazoacetic acid ester was found to be catalyzed by the copper complex of (7R,7'R)-7,7'-di(1-tert-butyldimethylsiloxy-1-methylethyl)-6,6',7,7'-tetrahydro-5H,5'H-2,2'-bi-1,1'-pyrindine (4). For example, the reaction of (R)-2-phenyloxetane of 89% ee and tert-buryl diazoacetate with Cu-4 complex as a catalyst provided (2S,3R)-tert-butyl 3-phenyltetrahydrofuran-2-carboxylate of 92% ee as a major product, while that of (S)-2-phenyloxetane of 85% ee provided (2S,3S)-tert-butyl 3-phenyltetrahydrofuran-2-carboxylate of 93% ee as a major one.

  DOI：

  10.3987/com-95-s35

文献信息

• Asymmetric Carbene C–O Insertion Reaction Using Optically Active Bipyridine-Copper Complex as a Catalyst. Ring Expansion of Oxetanes to Tetrahydrofurans
  作者：Katsuji Ito、Tsutomu Katsuki

  DOI：10.1246/cl.1994.1857

  日期：1994.10

  Copper complex of (7R,7R′)-7,7′-di(1-t-butyldimethylsiloxy-1-methylethyl)-6,6′,7,7′-tetrahydro-5H,5′H-2,2′-bi-1,1′-pyrindine (3) was found to be an effective catalyst for asymmetric carbene insertion reaction into the C-O bond of oxetanes. For example, the reaction of dl-2-phenyloxetane and t-butyl diazoacetate in the presence of Cu-3 complex provided trans- and cis-t-butyl 3-phenyltetrahydrofuran-2-carboxylate of 75% ee and 81% ee, respectively.

  (7R,7R′)-7,7′-二(1-t-丁基二甲基硅氧基-1-甲基乙基)-6,6′,7,7′-四氢-5H,5′H-2,2′-双-1,1′-吡啶铜复合物（3）被发现是一种有效的催化剂，用于不对称氮气插入反应进入氧杂环的C-O键。例如，dl-2-苯氧杂环与t-丁基二硝基乙酸酯在Cu-3复合物存在下的反应，分别提供了75%和81%对映体过剩的反-和顺- t-丁基 3-苯基四氢呋喃-2-羧酸酯。