anti-methyl 3-hydroxy-2,4,4-trimethylpentanoate | 71699-39-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: anti-methyl 3-hydroxy-2,4,4-trimethylpentanoate
• 英文别名: methyl 3-hydroxy-2,4,4-trimethylpentanoate；α,β-anti-methyl 3-hydroxy-2,4,4-trimethylpentanoate；methyl (2R,3S)-3-hydroxy-2,4,4-trimethylpentanoate
• CAS: 71699-39-3；71699-40-6；78655-81-9；78655-83-1；82545-52-6；92999-39-8；116183-30-3；148091-53-6
• 化学式: C₉H₁₈O₃
• 分子量: 174.24
• InChiKey: JTDNDDNQCCLINU-RQJHMYQMSA-N

物化性质

• 沸点：
  241.1±13.0 °C(Predicted)
• 密度：
  0.974±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (3R,4S)-4-tert-Butyl-2,2-dimethoxy-3-methyl-oxetane 在 甲醇 、 对甲苯磺酸 作用下， 以 异丙醚 为溶剂， 生成 anti-methyl 3-hydroxy-2,4,4-trimethylpentanoate
  参考文献：
  名称：

  Hofstraat, Rob G.; Scheeren, Hans W.; Nivard, Rutger J. F., Journal of the Chemical Society. Perkin transactions I, 1985, p. 561 - 564

  摘要：

  DOI：

文献信息

• Ti-direct, powerful, stereoselective aldol-type additions of esters and thioesters to carbonyl compounds: application to the synthesis and evaluation of lactone analogs of jasmone perfumes
  作者：Ryohei Nagase、Noriaki Matsumoto、Kohei Hosomi、Takahiro Higashi、Syunsuke Funakoshi、Tomonori Misaki、Yoo Tanabe

  DOI：10.1039/b613544g

  日期：——

  thiophenyl esters or thioaryl esters with aldehydes and ketones was performed (total 46 examples). The present method is advantageous from atom-economical and cost-effective viewpoints; good to excellent yields, moderate to good syn-selectivity, substrate variations, reagent availability, and simple procedures. Utilizing the present reaction as the key step, an efficient short synthesis of three lactone

  进行了有效的TiCl（4）-Et（3）N或Bu（3）N促进的醛和酮与苯和硫代苯基酯或硫代芳基酯的醛醇型加成反应（共46例）。从原子经济和成本有效的观点来看，本发明的方法是有利的。从良好到优异的产率，中等到良好的同选选择性，底物变化，试剂的可获得性和简单的程序。利用本反应作为关键步骤，进行了茉莉花香精的三种内酯[2（5H）-呋喃酮]类似物的有效短合成。其中，顺式茉莉酮的内酯类似物具有独特的香料特性（tabac）。
• Stereoselectivity in the aldol reaction
  作者：A.I. Meyers、Yukio Yamamoto

  DOI：10.1016/0040-4020(84)80014-9

  日期：1984.1

  Chiral oxazolines, as their boron enolates derived from various boron triflates, react with aldehydes to give erythro-selectivity (97% + %) with enantiomeric purities of 50–60%. Achiral oxazolines as their boron enolates derived from diisopinocampheylborane give, on reaction with aldehydes, β-hydroxy esters with high threo-selectivity (90+%) in 77–85% ee. A variety of structurally different oxazolines

  手性恶唑啉是源自三氟甲磺酸三氟硼烷的硼烯酸酯，它与醛反应生成对映异构体纯度为50-60％的赤型选择性（97％+％）。非手性恶唑啉作为二异硫代樟脑硼烷的硼烯酸酯，与醛反应后，在77–85％ee中具有高苏式选择性（90％以上）的β-羟基酯。还研究了各种结构不同的恶唑啉，其中许多显示出高的赤型选择性。
• Enantioselective aldol reactions with high threo or erythro selectivity using boron azaenolates
  作者：A. I. Meyers、Yukio Yamamoto

  DOI：10.1021/ja00404a064

  日期：1981.7
• Catalysis of the Mukaiyama aldol reaction using cationic zirconocene complexes
  作者：Yaping Hong、Derek J. Norris、Scott Collins

  DOI：10.1021/jo00065a027

  日期：1993.6
• Mukaiyama Aldol Reactions Catalyzed by Zirconocene Bis(triflate) Complexes:  Stereochemistry and Mechanisms for C−C Bond Formation
  作者：Shuqiong Lin、Georgiy V. Bondar、Christopher J. Levy、Scott Collins

  DOI：10.1021/jo971803g

  日期：1998.3.1

  The aldol condensations of alpha- and beta-(benzyloxy) aldehydes with enol silanes, catalyzed by Cp2Zr(OTf)(2) . THF or Cp2Zr(OTf)(2), in a variety of solvents were studied. The simple diastereoselectivity of these reactions is modest and comparable to that observed using simple aldehydes of similar steric requirements. Studies have revealed that TMSOTf is directly produced on reaction with the zirconocene catalyst with the enol silane in nitroalkane solvent or is formed during catalysis in dichloromethane solution. Although TMSOTf is known to catalyze cross-aldol reactions under these conditions, the rate of this process is not always competitive with that observed using the zircanocene catalysts. In particular, sterically unhindered or aromatic aldehydes react via a mechanism that appears to be mainly Zr-catalyzed, based on both the difference in rate between Zr- and Si-mediated reactions as well as differences in enol silane/silyl triflate reactivity in crossover-type experiments. With sterically hindered aldehydes in dichloromethane or nitromethane, catalysis is mediated by Si. The Zr-catalyzed process occurs via formation of a Zr-aldolate complex from aldehyde and enol silane, with liberation of TMSOTf, followed by rate-limiting O-silylatian of the metal aldolate by TMSOTf, as revealed by both model studies and in situ monitoring during catalysis.