(-)-(S)-4-methylcyclohexene | 591-47-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (-)-(S)-4-methylcyclohexene
• 英文别名: (S)-(-)-4-methylcyclohexene；(S)-4-methylcyclohexene；(4S)-methylcyclohexene；(S)-4-methyl-cyclohexene；4-Methyl-cyclohexen；(4S)-4-methylcyclohexene
• CAS: 591-47-9；5710-02-1；26293-22-1；5681-54-9
• 化学式: C₇H₁₂
• 分子量: 96.1723
• InChiKey: FSWCCQWDVGZMRD-SSDOTTSWSA-N

物化性质

• 沸点：
  104.3±7.0 °C(Predicted)
• 密度：
  0.803±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 危险品标志：
  Xn,F
• 安全说明：
  S16,S26,S29,S36,S62,S9
• 危险类别码：
  R36/37/38,R65,R11
• WGK Germany：
  3
• 危险品运输编号：
  UN 3295 3/PG 2
• 包装等级：
  II
• 危险类别：
  3.1

反应信息

• 作为反应物：
  描述：

  (-)-(S)-4-methylcyclohexene 在 sodium azide 、 三氟乙酸 作用下， 以 乙腈 为溶剂， 反应 3.0h， 生成 4-methyl-trans-1,2-diazidocyclohexane
  参考文献：
  名称：

  甲基取代的反式-1,2-环己二胺作为奥沙利铂型配合物的新配体

  摘要：

  提出了三种不同的途径合成取代的反式-（±）-1,2-环己二胺作为奥沙利铂类化合物的新配体。不同的合成路线导致（i）通过取代环己酮的邻溴化合成化合物，然后与羟胺反应并用氢还原，（ii）通过将乙酸锰（III）介导的叠氮化物加到环己烯中并还原通过氢，或（iii）通过环己烯的反二羟基化，然后转化成各自的甲磺酸酯或甲苯磺酸酯，随后被叠氮化物取代，和在4-甲基-反式的情况下还原-（±）-1,2-环己二胺分别优选在赤道上，主要在轴向上或仅在赤道上或轴向上定向的4-甲基。

  DOI：

  10.1016/j.tet.2007.10.069
• 作为产物：
  描述：

  (+)-香茅醛 在 三氯化铝 、 RhCl(PPh₃)3 、 三苯基膦 作用下， 以 四氢呋喃 、 异丙醇 为溶剂， 生成 (-)-(S)-4-methylcyclohexene
  参考文献：
  名称：

  使用多种过渡金属合成烯烃的多催化过程

  摘要：

  描述了从醇合成烯烃的一系列级联过程。每个单独的步骤都由特定的过渡金属络合物催化。氧化-亚甲基化一锅法在钯和铑催化剂存在下进行，以高产率生产所需的末端烯烃。使用第二代复分解催化剂，甲基化-闭环复分解允许从羰基衍生物合成环状烯烃。最后，介绍了在同一容器中最多包含三种不同过渡金属催化剂的氧化-甲基化-RCM 工艺。

  DOI：

  10.1021/ja0472681

文献信息

• Enantioselective Synthesis of Chiral Sulfones by Ir-Catalyzed Asymmetric Hydrogenation: A Facile Approach to the Preparation of Chiral Allylic and Homoallylic Compounds
  作者：Taigang Zhou、Byron Peters、Matías F. Maldonado、Thavendran Govender、Pher G. Andersson

  DOI：10.1021/ja306731u

  日期：2012.8.22

  A highly efficient and enantioselective Ir-catalyzed hydrogenation of unsaturated sulfones was developed. Chiral cyclic and acyclic sulfones were produced in excellent enantioselectivities (up to 98% ee). Coupled with the Ramberg-Bäcklund rearrangement, this reaction offers a novel route to chiral allylic and homoallylic compounds in excellent enantioselectivities (up to 97% ee) and high yields (up

  开发了一种高效且对映选择性 Ir 催化的不饱和砜加氢反应。以优异的对映选择性（高达 98% ee）生产手性环状和无环砜。与 Ramberg-Bäcklund 重排相结合，该反应提供了一种获得具有优异对映选择性（高达 97% ee）和高产率（高达 94%）的手性烯丙基和同型烯丙基化合物的新途径。
• Practical catalyst for cyclic metathesis. Synthesis of functional and/or enantiopure cycloalkenes.
  作者：William A. Nugent、Jerald Feldman、Joseph C. Calabrese

  DOI：10.1021/ja00140a015

  日期：1995.9

  The oxo-tungsten complex trans-WOCl2(OAr)(2) (Ar = 2,6-dibromophenyl) is prepared by reaction of WOCl4 with 2 equiv of 2,6-dibromophenol. A variety of nonconjugated dienes are cleanly cyclized to the corresponding cycloalkenes using 2 mol % of this catalyst in combination with 4 mol % of tetraethyllead. All three components of the catalyst system are commercially available. The catalytic reactions are typically complete in 1 h at 90 degrees C and allow the synthesis of chiral cycloalkenes with little or no loss in optical activity. For example, (R)- (S)-citronellene have been cyclized to the corresponding (R)- or (S)-3-methylcyclopentenes in 97% enantiomeric excess. The cyclization is compatible with a variety of functional groups including some eater, amide, and ether derivatives. Tri- (but not tetra-) substituted cycloalkenes could be prepared using this catalyst.
• {(1<i>R</i>,2<i>R</i>,4<i>R</i>)-4-Methyl-1,2-cyclohexanediamine}oxalatoplatinum(II): A Novel Enantiomerically Pure Oxaliplatin Derivative Showing Improved Anticancer Activity in Vivo
  作者：Sergey A. Abramkin、Ute Jungwirth、Seied M. Valiahdi、Claudia Dworak、Ladislav Habala、Kristof Meelich、Walter Berger、Michael A. Jakupec、Christian G. Hartinger、Alexey A. Nazarov、Mathea Sophia Galanski、Bernhard K. Keppler

  DOI：10.1021/jm100953c

  日期：2010.10.28

  Novel derivatives of the clinically established anticancer drug oxaliplatin were synthesized. Cytotoxicity of the compounds was studied in six human cancer cell lines by means of the MTT assay. Additionally, most promising complexes were also investigated in cisplatin- and oxaliplatin-resistant human cancer cell models. The therapeutic efficacy in vivo was studied in the murine L1210 leukemia model. Most remarkably, (1R,2R,4R)-4-methyl-1,2-cyclohexanediamine}oxalatoplatinum(II), comprising an equatorial methyl substituent at position 4 of the cyclohexane ring, was as potent as oxaliplatin in vitro but distinctly more effective in the L1210 model in vivo at the optimal dose. The advantage observed in the in vivo situation was mainly based on a more favorable therapeutic index. The maximum tolerated dose of the novel analogue was higher than that of oxaliplatin and caused a greater increase in life span (>200% versus 152%), with more animals experiencing long-term survival (5/6 versus 2/6). These data support further (pre)clinical development of the methyl-substituted oxaliplatin analogue with improved anticancer activity.
• Methyl-substituted trans-1,2-cyclohexanediamines as new ligands for oxaliplatin-type complexes
  作者：Ladislav Habala、Claudia Dworak、Alexey A. Nazarov、Christian G. Hartinger、Sergey A. Abramkin、Vladimir B. Arion、Wolfgang Lindner、Mathea S. Galanski、Bernhard K. Keppler

  DOI：10.1016/j.tet.2007.10.069

  日期：2008.1

  different synthetic routes lead (i) by the synthesis of the compound via ortho-bromination of a substituted cyclohexanone followed by reaction with hydroxylamine and reduction by hydrogen, (ii) by addition of azide to cyclohexene mediated by manganese(III) acetate and reduction by hydrogen, or (iii) by trans-dihydroxylation of cyclohexene, and subsequent conversion into the respective mesylate or tosylate

  提出了三种不同的途径合成取代的反式-（±）-1,2-环己二胺作为奥沙利铂类化合物的新配体。不同的合成路线导致（i）通过取代环己酮的邻溴化合成化合物，然后与羟胺反应并用氢还原，（ii）通过将乙酸锰（III）介导的叠氮化物加到环己烯中并还原通过氢，或（iii）通过环己烯的反二羟基化，然后转化成各自的甲磺酸酯或甲苯磺酸酯，随后被叠氮化物取代，和在4-甲基-反式的情况下还原-（±）-1,2-环己二胺分别优选在赤道上，主要在轴向上或仅在赤道上或轴向上定向的4-甲基。
• Multicatalytic Processes Using Diverse Transition Metals for the Synthesis of Alkenes
  作者：Hélène Lebel、Valérie Paquet

  DOI：10.1021/ja0472681

  日期：2004.9.1

  A series of cascade processes for the synthesis of alkenes from alcohols is described. Each individual step is catalyzed with a specific transition metal complex. The oxidation-methylenation one-pot procedure took place in the presence of a palladium and a rhodium catalyst to produce the desired terminal alkenes in high yields. A methylenation-ring-closing metathesis allowed the synthesis of cyclic

  描述了从醇合成烯烃的一系列级联过程。每个单独的步骤都由特定的过渡金属络合物催化。氧化-亚甲基化一锅法在钯和铑催化剂存在下进行，以高产率生产所需的末端烯烃。使用第二代复分解催化剂，甲基化-闭环复分解允许从羰基衍生物合成环状烯烃。最后，介绍了在同一容器中最多包含三种不同过渡金属催化剂的氧化-甲基化-RCM 工艺。