(Z)-2,2-Dimethyl-3-pentanone enolate | 130525-24-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-2,2-Dimethyl-3-pentanone enolate
• 英文别名: 2,2-dimethyl-pentan-3-one; (Z)-enol form；(Z)-4,4-dimethyl-pent-2-en-3-ol；(Z)-4,4-dimethylpent-2-en-3-ol
• CAS: 130525-24-5
• 化学式: C₇H₁₄O
• 分子量: 114.188
• InChiKey: FSEKBMBFMVLODB-WAYWQWQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-2,2-Dimethyl-3-pentanone enolate 在 (+)-tetrahydro-9,9-dimethyl-4H-4a,7-methanooxazirino<3,2-i><2,1>benzisothiazole 3,3-dioxide 、 sodium hexamethyldisilazane 作用下， 生成 (S)-(+)-4-hydroxy-2,2-dimethyl-3-pentanone 、 (R)-(-)-4-Hydroxy-2,2-dimethyl-3-pentanone
  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

• 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.