3,3-dibromocamphorsulphonylimine | 131878-45-0

• 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: 3,3-dibromocamphorsulphonylimine
• 英文别名: (3aS)-7,7-dibromo-8,8-dimethyl-4,5,6,7-tetrahydro-3a,6-methano-benz[c]isothiazole-2,2-dioxide；(3aS)-7,7-Dibrom-8,8-dimethyl-4,5,6,7-tetrahydro-3a,6-methano-benz[c]isothiazol-2,2-dioxid；(1S,7S)-6,6-dibromo-10,10-dimethyl-3lambda6-thia-4-azatricyclo[5.2.1.01,5]dec-4-ene 3,3-dioxide；(1S,7S)-6,6-dibromo-10,10-dimethyl-3λ6-thia-4-azatricyclo[5.2.1.01,5]dec-4-ene 3,3-dioxide
• CAS: 131878-45-0
• 化学式: C₁₀H₁₃Br₂NO₂S
• 分子量: 371.093
• InChiKey: NQCMAOHWZFXROF-IMTBSYHQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  54.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,3-dibromocamphorsulphonylimine 在 potassium carbonate 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以60%的产率得到3,3-dibromocamphorsulphonyloxaziridine
  参考文献：
  名称：

  氧氮杂环丙烷的多核磁共振研究

  摘要：

  比较了各种恶氮丙啶的三个环原子的 NMR 数据（13C、15N、17O）。讨论了它们对预测手性恶氮丙啶氧化硫化物的对映选择性的重要性。

  DOI：

  10.1002/mrc.1260310509
• 作为产物：
  描述：

  (+/-)-8,8-dimethyl-4,5,6,7-tetrahydro-3ar,6c-methano-benz[c]isothiazole-2,2-dioxide 在 N-溴代丁二酰亚胺(NBS) 、 sodium hexamethyldisilazane 作用下， 生成 3,3-dibromocamphorsulphonylimine
  参考文献：
  名称：

  Chemistry of oxaziridines. 18. Synthesis and enantioselective oxidations of the [(8,8-dihalocamphoryl)sulfonyl]oxaziridines

  摘要：

  The synthesis and enantioselective oxidations of [(8,8-dihalocamphoryl)sulfonyl]oxaziridines [8,8-dichloro-1,7,7-trimethyl-2'-(phenylsulfonyl)spiro[bicyclo[2.2.1]heptane-2,3'-oxazinidine]] 13 are reported. These reagents are prepared in two steps from the (camphorylsulfonyl)imine 4 by treatment of the corresponding azaenolate with electrophilic halogen sources followed by biphasic oxidation of the resulting dihalo imine 6-9 with m-CPBA/K2CO3. Of these oxaziridines the dichloro reagent 13b, available on a multigram scale, affords the highest enantioselectivities for the asymmetric oxidation of sulfides to sulfoxides (42-74%) and for the hydroxylation of enolates (often better than 95% ee). In general the molecular recognition is predicted and explained in terms of minimization of nonbonded steric interactions the transition states. For the asymmetric oxidation of sulfides to sulfoxides, secondary electronic factors related to the polarity of the sulfide and oxaziridine also play a role. Definitive evidence for chelation of the metal enolate with the C-X bond in 13 is not found. The molecular recognition is interpreted in terms of the higher reactivity of the reagents and an active-site structure which is sterically complementary with the enolate. For the asymmetric hydroxylation of the Z- and E-enolates of propiophenone (16a), the Z-enolate exhibits much higher stereoselectivity than the E-enolate: >95% vs 22% ee.

  DOI：

  10.1021/jo00052a050

文献信息

• Armstrong; Lowry, Journal of the Chemical Society, 1902, vol. 81, p. 1449
  作者：Armstrong、Lowry

  DOI：——

  日期：——
• Multinuclear magnetic resonance study of oxaziridines
  作者：Mane Čudić、Rudolf Herrmann

  DOI：10.1002/mrc.1260310509

  日期：1993.5

  NMR data (13C, 15N, 17O) for the three ring atoms of various oxaziridines are compared. Their significance for the prediction of the enantioselectivity of the oxidation of sulphides by chiral oxaziridines is discussed.

  比较了各种恶氮丙啶的三个环原子的 NMR 数据（13C、15N、17O）。讨论了它们对预测手性恶氮丙啶氧化硫化物的对映选择性的重要性。
• Chemistry of oxaziridines. 18. Synthesis and enantioselective oxidations of the [(8,8-dihalocamphoryl)sulfonyl]oxaziridines
  作者：Franklin A. Davis、Michael C. Weismiller、Christopher K. Murphy、R. Thimma Reddy、Band Chi Chen

  DOI：10.1021/jo00052a050

  日期：1992.12

  The synthesis and enantioselective oxidations of [(8,8-dihalocamphoryl)sulfonyl]oxaziridines [8,8-dichloro-1,7,7-trimethyl-2'-(phenylsulfonyl)spiro[bicyclo[2.2.1]heptane-2,3'-oxazinidine]] 13 are reported. These reagents are prepared in two steps from the (camphorylsulfonyl)imine 4 by treatment of the corresponding azaenolate with electrophilic halogen sources followed by biphasic oxidation of the resulting dihalo imine 6-9 with m-CPBA/K2CO3. Of these oxaziridines the dichloro reagent 13b, available on a multigram scale, affords the highest enantioselectivities for the asymmetric oxidation of sulfides to sulfoxides (42-74%) and for the hydroxylation of enolates (often better than 95% ee). In general the molecular recognition is predicted and explained in terms of minimization of nonbonded steric interactions the transition states. For the asymmetric oxidation of sulfides to sulfoxides, secondary electronic factors related to the polarity of the sulfide and oxaziridine also play a role. Definitive evidence for chelation of the metal enolate with the C-X bond in 13 is not found. The molecular recognition is interpreted in terms of the higher reactivity of the reagents and an active-site structure which is sterically complementary with the enolate. For the asymmetric hydroxylation of the Z- and E-enolates of propiophenone (16a), the Z-enolate exhibits much higher stereoselectivity than the E-enolate: >95% vs 22% ee.