(3S)-3-butyl-2-methylidenecyclohexan-1-one | 124482-31-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3S)-3-butyl-2-methylidenecyclohexan-1-one
• CAS: 124482-31-1
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: ALIGEXIYMVDPIJ-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3S)-3-butyl-2-methylidenecyclohexan-1-one 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 (2R,3S)-3-Butyl-2-phenylsulfanylmethyl-cyclohexanone
  参考文献：
  名称：

  Stereoselective synthesis of cis 2,3-disubstituted cycloheptanones by kinetic protonation

  摘要：

  The hitherto unknown stereochemistry concerning the formation of 2,3-disubstituted cycloheptanones by the Michael addition reaction was studied. The Michael addition of thiophenol to 3-substituted 2-methylene-cycloheptanones in the presence of triethylamine in THF at ambient temperature produced 3-substituted 2-[(phenylthio)methyl]cycloheptanones with high cis selectivity (>96/4), which was unequivocally established by H-1 NMR and X-rays analyses. An isomerization experiment and theoretical calculations (AM1) suggest that the origin of the observed high stereoselectivity can be explained in terms of kinetic protonation of the corresponding enolate intermediate.

  DOI：

  10.1021/jo00044a027
• 作为产物：
  描述：

  2-(硝基甲基)-环己-1-烯-3-酮 在 lithium bromide 作用下， 以 乙腈 为溶剂， 反应 2.17h， 生成 (3S)-3-butyl-2-methylidenecyclohexan-1-one
  参考文献：
  名称：

  Asymmetric synthesis of 3-substituted 2-exo-methylenealkanones by addition-elimination reaction using a chiral leaving group and organometallic nucleophiles

  摘要：

  A novel diastereodifferentiating addition-elimination reaction of (S)-2-[[2-(methoxymethyl)-1-pyrrolidinyl]methyl]-2-alken-1-ones with organometallic reagents such as organocuprates and organozincates afforded optically active 3-substituted 2-methylenealkanones with high enantiomeric purity. The enantiomeric excess (ee) of the products in this asymmetric induction reaction involving 1,5-transfer of stereogenicity was highly dependent on the structure of the enone substrates and the type of organometallic reagents, chiral auxiliaries, and added Lewis acids: (i) the use of lithium diorganocuprates (R2CuLi) led to the highest ee's, (ii) in the reaction with R2CuLi the ee decreased in the following order by varying their structure of the main framework of the enones, cycloheptenones (96-97% ee) > cyclohexenones (95% ee) > cyclopentenones (82-85% ee) > acyclic enones (55-70% ee), (iii) the addition of LiBr as the external Lewis acid in the reaction with R2CuLi did not affect the ee, whereas that of ZnBr2 or MgBr2 decreased the ee by 5% or considerably more, respectively, and (iv) the existence of the methoxy oxygen atom in the chiral auxiliary was essential to achieve high ee's. The origin of the observed high and low ee's was rationalized by considering plausible transition state models.

  DOI：

  10.1021/jo00044a026

文献信息

• Asymmetric synthesis of 3-substituted-2-exo-methylenecyclohexanones via 1,5-diastereoselection by using a chiral amine
  作者：Rui Tamura、Kenichiro Watabe、Hitoshi Katayama、Hitomi Suzuki、Yukio Yamamoto

  DOI：10.1021/jo00289a003

  日期：1990.1
• TAMURA, RUI;WATABE, KEN-ICHIRO;KATAYAMA, HITOSHI;SUZUKI, HITOMI;YAMAMOTO,+, J. ORG. CHEM., 55,(1990) N, C. 408-410
  作者：TAMURA, RUI、WATABE, KEN-ICHIRO、KATAYAMA, HITOSHI、SUZUKI, HITOMI、YAMAMOTO,+

  DOI：——

  日期：——