(-)-((8,8-Dichlorocamphoryl)sulfonyl)imine | 139628-15-2

• 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: (-)-[(8,8-Dichlorocamphoryl)sulfonyl]imine；(1R,7R)-6,6-dichloro-10,10-dimethyl-3lambda6-thia-4-azatricyclo[5.2.1.01,5]dec-4-ene 3,3-dioxide；(1R,7R)-6,6-dichloro-10,10-dimethyl-3λ6-thia-4-azatricyclo[5.2.1.01,5]dec-4-ene 3,3-dioxide
• CAS: 139628-15-2
• 化学式: C₁₀H₁₃Cl₂NO₂S
• 分子量: 282.191
• InChiKey: OPVLQNKVOQBPIM-MUWHJKNJSA-N

物化性质

• 沸点：
  387.7±52.0 °C(Predicted)
• 密度：
  1.69±0.1 g/cm3(Predicted)

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 lithium aluminium tetrahydride 、 溴 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 氯仿 、 甲苯 为溶剂， 反应 10.0h， 生成 [3aR-[1(1S*,3aS*,6aR*),3aα,6α,7aβ]]-3H-3a,6-methano-2,1-benzisothiazole, 7,7-dichloro-4,5,6,7-tetrahydro-8,8-dimethyl-1-[[octahydro-4,6-dioxo-5-phenyl-2-(phenylmethyl)pyrrolo[3,4-c]pyrrol-1-yl]carbonyl]-2,2-dioxide
  参考文献：
  名称：

  使用Oppolzer的樟脑sultam作为羰基稳定的偶氮甲碱烷基化物的手性助剂，进行立体控制的1,3-偶极环加成反应

  摘要：

  描述了通过手性偶氮甲亚胺基团的立体控制的1，3-偶极环加成反应来取代吡咯烷的两种互补方法。在一种方法中，通过将氮丙啶羧酸酯的sultams热解产生手性的甲亚胺基团，并用多种偶极亲和剂捕获，以得到相应环加合物的良好收率。在第二种方法中，通过“亚胺互变异构化”从甘氨酰磺胺生成手性偶氮甲亚胺，并用双极性亲和剂捕获，得到相应环加合物的良好收率。

  DOI：

  10.1016/s0040-4020(00)00998-4
• 作为产物：
  描述：

  (+)-(3-Oxocamphorsulfonyl)imine 在 硫酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 、 乙酸乙酯 为溶剂， 反应 6.0h， 生成 (-)-((8,8-Dichlorocamphoryl)sulfonyl)imine
  参考文献：
  名称：

  (+)-(2R,8aR)-[(8,8-DIMETHOXYCAMPHORYL)SULFONYL]OXAZIRIDINE AND (+)-(2R,8aR)-[(8,8-DICHLOROCAMPHORYL)SULFONYL]OXAZIRIDINE

  摘要：

  DOI：

  10.15227/orgsyn.073.0159

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％。
• Total chiral synthesis of azole antifungals via α-hydroxylation of ketones
  作者：Dinesh Gala、Donald J. DiBenedetto、Ingrid Mergelsberg、Max Kugelman、Schering-Plough Research

  DOI：10.1016/0040-4039(96)01887-4

  日期：1996.11

  The use of camphorsulfonyl oxaziridines for the preparation of 2′,4′-difluoro-(R)-2-hydroxypropiophenone, (2), a key intermediate for the synthesis of azole antifungals Sch 42427 and ER-30346 (1) in excellent enantiomeric excess and high chemical yield is described.

  樟脑磺酰基恶唑烷类在制备2'，4'-二氟-（R）-2-羟基丙苯酮中的用途（2），这是合成优异抗对映异构体的唑类抗真菌剂Sch 42427和ER-30346的关键中间体（1）描述了过量和高化学产率。
• 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.
• 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.