(1S,2R,4R,S_S)-7,7-dimethyl-N-(phenylmethylene)-2-(trimethylsilyloxy)bicyclo[2.2.1]heptane-1-methanesulfinamide | 253665-35-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,2R,4R,S_S)-7,7-dimethyl-N-(phenylmethylene)-2-(trimethylsilyloxy)bicyclo[2.2.1]heptane-1-methanesulfinamide
• 英文别名: (NE,S)-N-benzylidene-1-[(1S,2R,4R)-7,7-dimethyl-2-trimethylsilyloxy-1-bicyclo[2.2.1]heptanyl]methanesulfinamide
• CAS: 253665-35-9
• 化学式: C₂₀H₃₁NO₂SSi
• 分子量: 377.623
• InChiKey: ODQNGASJOBPUHA-VJSOCDGRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  57.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2R,4R,S_S)-7,7-dimethyl-N-(phenylmethylene)-2-(trimethylsilyloxy)bicyclo[2.2.1]heptane-1-methanesulfinamide 在 镍 三氟甲磺酸三甲基硅酯 、 zinc trifluoromethanesulfonate 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 19.33h， 生成 6-phenylpiperidin-2-one
  参考文献：
  名称：

  Addition of dienolates to sulfinimines. Stereoselective synthesis of dihydropyridones

  摘要：

  The vinylogous Mannich reaction of sulfinimines with dienolates was investigated. Lithium and trimethylsilyl enolates of ethyl 3-ethoxycrotonate reacted with enantiopure 10-isobornylsulfinimines to give derivatives of delta -aminoacids which were cyclised to 6-aryl substituted derivatives of 2(1H)-pyridinones. 6-Aryl substituted 2,4-piperidinediones with either (S) or (R) configuration were analogously obtained using lithium and TMS enolates of 2,2,6-trimethyl-1,3-dioxin-4-one. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00833-x
• 作为产物：
  描述：

  (1S,5R,7R,S_S)-10,10-dimethyl-4-oxo-3-thiatricyclo[5.2.1.0^1,5]decane-3-oxide 在 正丁基锂 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 5.0h， 生成 (1S,2R,4R,S_S)-7,7-dimethyl-N-(phenylmethylene)-2-(trimethylsilyloxy)bicyclo[2.2.1]heptane-1-methanesulfinamide
  参考文献：
  名称：

  Lewis Acid Mediated Addition of Silyl Ketene Acetals to Sulfinimines

  摘要：

  DOI：

  10.1021/jo990913f

文献信息

• Aza Diels–Alder reactions of sulfinimines with the Rawal diene
  作者：Robert Kawęcki

  DOI：10.1016/j.tetasy.2006.04.026

  日期：2006.5

  The aza Diels–Alder reaction of optically active sulfinimines with the Rawal diene leads to enantiomerically enriched dihydropyridones with ees up to 90%. The reaction was catalyzed by TMSOTf. The best results were obtained using 10-isobornylsulfinimines. Removal of the sulfinyl auxiliary occurred during workup of the reaction mixture. The reaction most likely proceeds via a stepwise mechanism. The

  光学活性亚氨基亚胺与Rawal二烯的氮杂Diels-Alder反应导致对映体富集的二氢吡啶酮，其ee含量高达90％。该反应由TMSOTf催化。使用10-异冰片烷基亚磺胺可获得最佳结果。在反应混合物的后处理期间除去亚磺酰基助剂。该反应最有可能通过逐步机制进行。将4- N，N'- N'-二甲基氨基-1,3-丁烯-2-油酸锂加到亚磺胺中，然后水解，以较低的收率和相反的立体化学得到二氢吡啶酮。
• New, recoverable and highly effective sulfinyl chiral auxiliary
  作者：Robert Kawęcki

  DOI：10.1016/s0957-4166(03)00624-4

  日期：2003.9

  A facile synthesis of a bicyclic 8-menthylsulfinate is described. The reaction of this sultine with organometallic compounds leads to gamma-hydroxysulfoxides, while the reaction with lithium amide affords 8-menthylsulfinamide. The chiral efficiency of the 8-menthylsulfinyl auxiliary was tested in the reaction of sulfinimines with Grignard reagents. A highly stereoselective addition of ethylmagnesium bromide to 8-menthylsulfinimine was observed (98% de). (C) 2003 Elsevier Ltd. All rights reserved.