(4R,4aS,7aR)-4-methyl-7a-(((R)-N-methyl-S-phenylsulfonimidoyl)methyl)-hexahydrocyclopent[d][1,3]oxazin-2(1H)-one | 942598-45-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (4R,4aS,7aR)-4-methyl-7a-(((R)-N-methyl-S-phenylsulfonimidoyl)methyl)-hexahydrocyclopent[d][1,3]oxazin-2(1H)-one
• CAS: 942598-45-0
• 化学式: C₁₆H₂₂N₂O₃S
• 分子量: 322.428
• InChiKey: AAUJGTXFAYZATN-DCNSGQDGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  22.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  67.76
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (4R,4aS,7aR)-4-methyl-7a-(((R)-N-methyl-S-phenylsulfonimidoyl)methyl)-hexahydrocyclopent[d][1,3]oxazin-2(1H)-one 在 正丁基锂 、 1-氯乙基氯甲酸酯 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 60.0h， 生成 (3aS,4R,11S,11aR)-11-chloro-4-methyl-2,3,3a,4,8,9,10,11-octahydrocyclopenta[d]pyrido[1,2-c][1,3]oxazin-6(1H)-one
  参考文献：
  名称：

  Modular Asymmetric Synthesis of Functionalized Azaspirocycles Based on the Sulfoximine Auxiliary

  摘要：

  A modular asymmetric synthesis of the functionalized azaspirocycles 6 (m = 2, n = 1), 7 (m = 1, n = 2), 8 (m = n = 2), 12, 20, and 24 from the cyclic allylic sulfoximines 1 is described. The synthetic strategy is based on the stereoselective construction of the carbocycle 4 containing the amino-substituted tertiary C atom from 1 followed by the generation of the azaspirocycle. Three different routes have been followed for the synthesis of the heterocyclic ring: N,C-dianion cycloalkylation, ring-closing metathesis, and N-acyl iminium ion formation.

  DOI：

  10.1021/ol0706410
• 作为产物：
  描述：

  (R)-1-((1S,Z)-2-{[(R)-N-methylphenylsulfonimidoyl]methylene}cyclopentyl)ethyl carbamate 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 12.0h， 以1.56 g的产率得到(4R,4aS,7aR)-4-methyl-7a-(((R)-N-methyl-S-phenylsulfonimidoyl)methyl)-hexahydrocyclopent[d][1,3]oxazin-2(1H)-one
  参考文献：
  名称：

  Modular Asymmetric Synthesis of Functionalized Azaspirocycles Based on the Sulfoximine Auxiliary

  摘要：

  A modular asymmetric synthesis of the functionalized azaspirocycles 6 (m = 2, n = 1), 7 (m = 1, n = 2), 8 (m = n = 2), 12, 20, and 24 from the cyclic allylic sulfoximines 1 is described. The synthetic strategy is based on the stereoselective construction of the carbocycle 4 containing the amino-substituted tertiary C atom from 1 followed by the generation of the azaspirocycle. Three different routes have been followed for the synthesis of the heterocyclic ring: N,C-dianion cycloalkylation, ring-closing metathesis, and N-acyl iminium ion formation.

  DOI：

  10.1021/ol0706410

文献信息

• Sulfoximine-Based Modular Enantioselective Synthesis of Azaspirocycles Featuring Sulfoximine Displacement, Dianion Cycloalkylation, RCM and<i>N</i>-Acyliminium Ion Formation
  作者：Adeline Köhler née Adrien、Gerhard Raabe、Jan Runsink、Franz Köhler、Hans-Joachim Gais

  DOI：10.1002/ejoc.201400068

  日期：2014.6

  Ring-closing metathesis of a bicyclic C,N-dienyl derivative furnished the corresponding spirocycle with an unsaturated piperidine ring. Cyclisation of an acetal group containing bicyclic oxazinanone gave spirocycles containing O,N-acetal and enamide groups. The diastereoselective reaction of a spirocyclic O,N-acetal with an allylsilane furnished the corresponding spirocycle, carrying an allyl group at the

  我们描述了具有一系列环尺寸的功能化氮杂螺环的模块化、对映选择性合成。该合成利用了亚砜亚胺的特殊特性，包括手性、碳负离子稳定、亲核性和疏核性。通过氨基甲酸酯方法对羟烷基取代的环烯基亚砜亚胺进行非对映选择性分子内胺化得到含有氨基取代的叔 C 原子的双环恶嗪酮。用双亲电试剂对相应的 C,N-二价阴离子进行环烷基化得到亚砜亚胺取代的螺环。用具有双键和缩醛基团的官能化亲电试剂对 C,N-二价阴离子进行单烷基化，得到相应的 C-烷基化双环亚砜亚胺。通过卤甲酸酯反应置换双环和螺环亚砜亚胺的亚砜亚胺基团得到相应的卤化物（Cl，I）。双环卤化物与官能化铜酸盐的烷基化和亚砜亚胺取代的双环的还原，在 Cα 原子上带有一个烷基，为逐步构建杂环提供了起始材料。双环 C,N-二烯基衍生物的闭环复分解为相应的螺环提供了一个不饱和的哌啶环。含有双环恶嗪酮的缩醛基团的环化得到含有 O,N-缩醛和烯酰胺基团的螺环。螺环 O,