(+)-((8,8-Dichlorocamphoryl)sulfonyl)imine | 127184-04-7

• 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: (+)-((8,8-Dichlorocamphoryl)sulfonyl)imine
• 英文别名: (1S,7S)-6,6-dichloro-10,10-dimethyl-3lambda6-thia-4-azatricyclo[5.2.1.01,5]dec-4-ene 3,3-dioxide；(1S,7S)-6,6-dichloro-10,10-dimethyl-3λ6-thia-4-azatricyclo[5.2.1.01,5]dec-4-ene 3,3-dioxide
• CAS: 127184-04-7
• 化学式: C₁₀H₁₃Cl₂NO₂S
• 分子量: 282.191
• InChiKey: OPVLQNKVOQBPIM-IMTBSYHQSA-N

物化性质

• 沸点：
  387.7±52.0 °C(Predicted)
• 密度：
  1.69±0.1 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿、二氯甲烷

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 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：

  (+)-((8,8-Dichlorocamphoryl)sulfonyl)imine 在 potassium carbonate 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 8.0h， 以98%的产率得到(+)-8,8-二氯樟脑磺哑嗪
  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
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 氯 、 溶剂黄146 作用下， 生成 (+)-((8,8-Dichlorocamphoryl)sulfonyl)imine
  参考文献：
  名称：

  Armstrong; Lowry, Journal of the Chemical Society, 1902, vol. 81, p. 1449

  摘要：

  DOI：

文献信息

• A convenient, improved synthesis of (camphoryl)sulfonyl oxaziridines.
  作者：Ingrid Mergelsberg、Dinesh Gala、Dominik Scherer、Donald DiBenedetto、Marcus Tanner

  DOI：10.1016/0040-4039(92)88039-8

  日期：1992.1

  A convenient, efficient procedure for the large scale synthesis of chiral oxidizing reagents (+), and (−)-((8,8-dichlorocamphoryl)sulfonyl)oxaziridine, 5, as well as of 8,8 unsbustituted (+), and (−) (camphoryl)sulfonyl oxaziridine, 4, from (+), or (−) (camphorylsulfonyl)imine, 2, in step yields of 83% to 95%, is reported.

  用于大规模合成手性氧化剂（+）和（-）-（（8,8-二氯樟脑酰基）磺酰基）恶唑烷5和8,8未取代（+）的便捷高效的方法，以及据报道，（-）的（-）（樟脑酰基）磺酰基恶唑烷4，或（-）（樟脑酰基磺酰基）亚胺2，分步产率为83％至95％。
• ASYMMETRIC SYNTHESIS OF SULTAMS AND SULFONAMIDES VIA DIASTEREOSELECTIVE REDUCTION OF N-SULFONYLIMINES
  作者：Franklin A. Davis、Ping Zhou、Bang-Chi Chen

  DOI：10.1080/10426509608037955

  日期：1996.8.1

  The diastereoselective reduction of both cyclic and acyclic camphor sulfonylimines was investigated. With cyclic camphor sulfonylimines 1, reduction using NaBH4 in methanol afforded the corresponding camphorsultarns 2 in 92-95% yield as single diastereomers with the exception of Ic where debromination occurred prior to reduction. For the large scale preparation of camphorsultam la and its derivatives, important chiral auxiliaries in asymmetric synthesis, reduction with NaBH4 is the reagent of choice. Reduction of acyclic camphor sulfonylimines 7 to camphorsulfonamides 8 with the bulky reducing reagent, LiAl(OBu-i)(3)H afforded the highest de's (>90% de) and yields 90-95%.
• Asymmetric Fluorination of Enolates with Nonracemic <i>N</i>-Fluoro-2,10-Camphorsultams
  作者：Franklin A. Davis、Ping Zhou、Christopher K. Murphy、Gajendran Sundarababu、Hongyan Qi、Wei Han、Robert M. Przeslawski、Bang-Chi Chen、Patrick J. Carroll

  DOI：10.1021/jo972045x

  日期：1998.4.1

  The asymmetric "electrophilic" fluorination of tertiary enolates by nonracemic N-fluoro-2,10-camphorsultams 3 affords quaternary alpha-fluoro carbonyl compounds in modest yield and ee. The highest asymmetric induction was observed for the fluorination of the sodium enolate of 2-methyl-1-tetralone (8a) by (-)-N-fluoro-2,10-(3,3-dichlorocamphorsultam) (3b) to give (S)-(+)-2-fluoro-2-methyl-1-tetralone (9a) in 70% ee. The absolute configuration was established by X-ray crystallography of the corresponding diastereomeric beta-hydroxy sulfoximine prepared from (+/-)-9a and the Johnson reagent. The asymmetric induction exhibited by 3 is opposite to that of the closely related enolate hydroxylation reagents nonracemic (camphorylsulfonyl)oxaziridines 4. The N-fluoro sultams 3 were prepared by fluorination (10% F-2/N-2) of the corresponding sultams 5.
• Enantioselective synthesis of tertiary .alpha.-hydroxy carbonyl compounds using [(8,8-dichlorocamphoryl)sulfonyl]oxaziridine
  作者：Franklin A. Davis、Michael C. Weismiller

  DOI：10.1021/jo00299a007

  日期：1990.6
• Asymmetric fluorination of enolates with N-fluoro 2,10- (3,3-dichlorocamphorsultam)
  作者：Franklin A. Davis、Ping Zhou、Christopher K. Murphy

  DOI：10.1016/s0040-4039(00)60592-0

  日期：1993.6

  Asymmetric fluorination of enolates with nonracemic N-fluoro dichlorocamphorsultam 2b affords alpha-fluoro carbonyl compounds in good yield and up to 75% ee.