d-menthone enol TMS ether | 127129-06-0

• 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: d-menthone enol TMS ether
• 英文别名: (3S,6R)-3-methyl-6-(prop-2-yl)-1-trimethylsilyloxy-cyclohexene
• CAS: 127129-06-0
• 化学式: C₁₃H₂₆OSi
• 分子量: 226.434
• InChiKey: NWHSOZUHIDRDCH-NWDGAFQWSA-N

物化性质

• 沸点：
  221.6±8.0 °C(Predicted)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.42
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  d-menthone enol TMS ether 在 2,2,6,6-四甲基哌啶 、 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 叔丁基锂 、 碳酸氢钠 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 正戊烷 为溶剂， 反应 20.67h， 生成 (S)-7-isopropyl-2,3,6-trimethoxy-10-methyl-spiro[4.5]deca-2,6-diene-1,4-dione
  参考文献：
  名称：

  热诱导的环丁烯酮重排和多米诺骨牌反应。

  摘要：

  DOI：

  10.1002/anie.200603538
• 作为产物：
  描述：

  (+)-薄荷酮 在 2,2,6,6-四甲基哌啶 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.75h， 生成 d-menthone enol TMS ether
  参考文献：
  名称：

  热诱导的环丁烯酮重排和多米诺骨牌反应。

  摘要：

  DOI：

  10.1002/anie.200603538

文献信息

• Polymerization of<b><i>t</i></b>-Butyl Vinyl Ether Mediated by an Aluminum Lewis Acid–TrF System and Its Complex Structure–Tacticity Correlation
  作者：Masataka Oishi、Hisashi Yamamoto

  DOI：10.1246/bcsj.74.1445

  日期：2001.8

  A variety of aluminum (aryloxide)s were used with triphenylmethyl fluoride (TrF) initiator for the isoselective cationic polymerization of t-butyl vinyl ether. This contribution discusses the relationship between polymer tacticity and counteranion structure, which changed according to the bulkiness, strength and chirality of the Lewis acid combined with TrF so as to make the ionic pair more interactive

  多种铝（芳基氧化物）与三苯甲基氟（TrF）引发剂一起用于叔丁基乙烯基醚的等选择性阳离子聚合。该贡献讨论了聚合物立构规整度与抗衡阴离子结构之间的关系，其根据与 TrF 结合的路易斯酸的体积、强度和手性而变化，从而使离子对在聚合过程中更具相互作用。新开发的有机铝活化剂 15 和 22 的 mm = 55-57%，与非手性铝化合物相比，mm 增加了 10% 以上。
• Magnesium bis(diisopropylamide), a useful reagent for regio- and stereoselective synthesis of kinetic silyl enol ethers
  作者：Guillaume Lessène、Régis Tripoli、Philippe Cazeau、Claude Biran、Michel Bordeau

  DOI：10.1016/s0040-4039(99)00665-6

  日期：1999.5

  Less highly substituted silyl enol ethers are regiospecifically prepared in high yield, around room temperature under kinetic conditions, from unsymmetrical cyclic ketones and magnesium bis(diisopropylamide) [(DA)2Mg] in THF/heptane. This high regioselectivity is markedly higher than these reported for bromomagnesium diisopropylamide (DAMgBr); it is also similar to this of LDA/DME at −78°C, but (DA)2Mg

  在室温下，在动力学条件下，由不对称环酮和四氢呋喃/庚烷中的不对称环状酮和双（二异丙基酰胺）镁[（DA）2 Mg]区域特异性地制备高取代度较低的甲硅烷基烯醇醚。这种高的区域选择性显着高于溴镁二异丙基酰胺（DAMgBr）的报道。它也与LDA / DME在-78°C下的情况相似，但是（DA）2 Mg可以在室温下使用。另外，对于苄基酮观察到高的E-烯化立体选择性，这与用LDA获得的相反。
• Kinetic resolution of racemic 2-substituted cyclohexanones by enantioselective deprotonation
  作者：Hee-doo Kim、Hisashi Kawasaki、Makoto Nakajima、Kenji Koga

  DOI：10.1016/s0040-4039(01)89015-8

  日期：1989.1

  Incomplete deprotonation of racemic 2-substituted cyclohexanones (d1-4) by chiral lithium amides (2) in the presence of trimethylsilyl chloride was found to give the corresponding trimethylsilyl enol ethers (5) and the unreacted ketones (4) in reasonably high enantiomeric excesses.

  外消旋的2-取代的环己酮（D1-的不完全去质子化4）通过手性氨基化锂（2）中的三甲基氯硅烷的存在下，发现以得到相应的三甲基甲硅烷的烯醇醚（5）和未反应的酮（4在相当高的对映体过量） 。
• Dimethyldioxirane Oxidation of Titanium Enolates: Diastereoselective .alpha.-Hydroxylations
  作者：Waldemar Adam、Michael Mueller、Frank Prechtl

  DOI：10.1021/jo00088a015

  日期：1994.5

  The oxidation of titanium enolates, derived from a transmetalation reaction of the corresponding lithium enolates with (i-PrO)(3)TiCl, (Et(2)N)(3)TiCl, or Cp(2)TiCl(2), by dimethyldioxirane has been investigated. Furthermore, the diastereoselective hydroxylation of the chiral metal enolates, e.g., derived from camphor (1f), menthone (1g), flavanone (1h), and 2-benzylcyclopentanone (1i), by dimethyldioxirane has been examined. The diastereoselectivity of the oxygen transfer strongly depends on the metal partner coordinated to the enolate. The titanium enolates 4 resulted in much higher diastereoselectivities (up to 96% de) than the corresponding sodium enolates 5 and at least as high if not higher than the silyl enol ethers 6. Moreover, the aldol reaction of ester-derived sodium enolates with acetone, the unavoidable medium for dimethyldioxirane, could be totally suppressed by the use of the chlorotitanocene enolates 4. Thus, the oxidation of chiral titanium enolates by dimethyldioxirane represents a general, convenient, effective, and chemo- and diastereoselective synthesis of alpha-hydroxy carbonyl compounds.
• A highly convergent asymmetric synthesis of the C(19)-C(27) segment of rifamycin S: an application of enantiodifferentiating acetalization with menthone
  作者：Toshiro Harada、Yasuhiro Kagamihara、Sachi Tanaka、Kazuhiko Sakamoto、Akira Oku

  DOI：10.1021/jo00032a004

  日期：1992.3

  An enantiodifferentiating transformation of 1,3-alkanediols by kinetic acetalization with menthone is developed and used in a highly convergent asymmetric synthesis of the C(19)-C(27) segment of the ansa chain of rifamycin S.