t-2-Phenyl-c-2-(trimethylsiloxy)-r-1-cyclopropancarbonsaeure-methylester | 80737-54-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: t-2-Phenyl-c-2-(trimethylsiloxy)-r-1-cyclopropancarbonsaeure-methylester
• 英文别名: methyl (1S,2R)-2-phenyl-2-trimethylsilyloxycyclopropane-1-carboxylate
• CAS: 80737-54-8
• 化学式: C₁₄H₂₀O₃Si
• 分子量: 264.397
• InChiKey: RKECPCJERFWCHD-OCCSQVGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.93
• 重原子数：
  18.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  t-2-Phenyl-c-2-(trimethylsiloxy)-r-1-cyclopropancarbonsaeure-methylester 以72%的产率得到
  参考文献：
  名称：

  BRUCKNER CH.; REISS. IG, H.-U., CHEM. BER., 120,(1987) N 4, 617-626

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl (1R,2R)-2-phenyl-2-trimethylsilyloxycyclopropane-1-carboxylate 、 四氯化钛 生成 t-2-Phenyl-c-2-(trimethylsiloxy)-r-1-cyclopropancarbonsaeure-methylester
  参考文献：
  名称：

  REISSIG, H. -U.;BOEHM, I., TETRAHEDRON LETT., 1983, 24, N 7, 715-718

  摘要：

  DOI：

文献信息

• Enantioselectivity and<i>cis</i>/<i>trans</i>-Selectivity in Dirhodium(II)-Catalyzed addition of diazoacetates to olefins
  作者：Paul Müller、Corine Baud、Doïna Ené、Sharokh Motallebi、Michael P. Doyle、Bridget D. Brandes、Alexey B. Dyatkin、Marjorie M. See

  DOI：10.1002/hlca.19950780217

  日期：1995.3.22

  comparable. Additions catalyzed by 1 are strongly sensitive to steric effects. Highly substituted olefins afford cyclopropanes in only poor yield. The preferential cis-selectivity observed in reactions catalyzed by 1 is attributed to dominant interactions between the ligand of the catalyst and the substituents of both olefin and diazoacetate, which overrule the steric interactions between olefin and diazoacetate

  用[Rh 2 （4 S）-phox} 4 ]（1 ; phox =四[[4 S）-四氢-4-苯基恶唑-2-酮]）研究了Rh 11催化的重氮乙酸类酯类化合物向烯烃的加成反应。，[Rh 2 （（2 S）-mepy} 4 ]（2 ; mepy =四[甲基（2 S）-四氢-5-氧杂吡咯-2-羧酸酯]）和[Rh 2（OAc）4 ]（3）。当用2和3催化时，优先提供反式-环丙烷羧酸酯，顺式-异构体是1的主要产品。通常，用1和2获得的对映选择性是可比较的。1催化的加成对位阻效应非常敏感。高度取代的烯烃仅以较差的收率提供环丙烷。在1催化的反应中观察到的优先顺式选择性归因于催化剂的配体与烯烃和重氮乙酸酯的取代基之间的显性相互作用，该相互作用抵消了烯烃和重氮乙酸酯在过渡态下的卡宾转移的空间相互作用。
• Synthesis of Optically Active 2-Siloxycyclopropanecarboxylates by Asymmetric Catalysis, IV. – Influence of Nucleophilicity of Silyl Enol Ethers on Stereoselectivities in Asymmetric Cyclopropanation Reactions
  作者：Ralf Schumacher、Hans-Ulrich Reißig

  DOI：10.1002/jlac.199719970312

  日期：1997.3

  By variation of the aryl substituents of silyl enol ethers 1a–e and 1f–k, the influence of their nucleophilicity on the stereochemical outcome of cyclopropanation reactions was studied. Using the neutral Schiff-base catalyst 2 · Cu(OAc)2, there was only a weak effect. On the other hand, with the cationic bisoxazoline complex 3· CuOTf a remarkable increase in the enantioselectivity was observed with

  通过改变甲硅烷基烯醇醚1a–e和1f–k的芳基取代基，研究了它们的亲核性对环丙烷化反应立体化学结果的影响。使用中性席夫碱催化剂2 ·Cu（OAc）2，其作用很小。另一方面，对于阳离子双恶唑啉配合物3 ·CuOTf，在吸引电子的取代基（如三氟甲基或硝基）更强的情况下，对映选择性显着提高。
• Screening of Various Catalysts for the Asymmetric Cyclopropanation of Structurally Typical Silyl Enol Ethers—Scope and Limitations of Evans's Bisoxazoline Copper Catalyst
  作者：Ralf Schumacher、Hans-Ulrich Reißig、Franziska Dammast

  DOI：10.1002/chem.19970030418

  日期：1997.4

  AbstractThe scope and limitations of asymmetric syntheses of 2‐siloxycyclopropanecarboxylates 3 were examined by combination of structurally typical silyl enol ethers and methyl diazoacetate with various chiral catalysts. It was found that the Schiff base complex 5ṁCu(OAc)2 and the bisoxazoline complex 6ṁCuOTf gave the highest stereoselectivities (e.g., 72% ee for cis‐3d with 5ṁCu(OAc)2 as catalyst or 76% and 73% ee for cis‐ and trans‐3a, respectively, with 6‐CuOTf as catalyst). High enantioselectivities or diastereoselectivities were obtained. Other catalysts based on copper, rhodium or ruthenium complexes afforded significantly lower values. In further investigations, Evans's bisoxazoline complex 6‐CuOTf proved to be limited to 1,1‐disubstituted silyl enol ethers (e.g. 1a and 1e) for high enantiomeric excesses (up to > 95%, poor diastereoselectivities) and to 1,2‐substituted enol ethers (e.g. 1e) for high diastereoselectivities (cis:trans < 3:97, eetrans = 49%).
• Kunkel, Elisabeth; Reichelt, Ingrid; Reissig, Hans-Ulrich, Liebigs Annalen der Chemie, 1984, # 3, p. 512 - 530
  作者：Kunkel, Elisabeth、Reichelt, Ingrid、Reissig, Hans-Ulrich

  DOI：——

  日期：——
• High diastereoselection in the alkylation of siloxy-substituted methyl cyclopropanecarboxylates: consequence of a pyramidal ester enolate anion?
  作者：Hans Ulrich Reissig、Ingrid Boehm

  DOI：10.1021/ja00370a049

  日期：1982.3