methyl (4R*,5S*)-4,6-dimethyl-5-((tert-butyldimethylsilyl)oxy)-2(E)-heptenoate | 122236-71-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (4R*,5S*)-4,6-dimethyl-5-((tert-butyldimethylsilyl)oxy)-2(E)-heptenoate
• 英文别名: methyl (E,4S,5R)-5-[tert-butyl(dimethyl)silyl]oxy-4,6-dimethylhept-2-enoate
• CAS: 122236-71-9；122236-72-0；122330-73-8；122330-74-9
• 化学式: C₁₆H₃₂O₃Si
• 分子量: 300.514
• InChiKey: YBIPUHUWFWNNGC-VLMQMFMZSA-N

物化性质

• 沸点：
  325.5±25.0 °C(Predicted)
• 密度：
  0.902±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (4R*,5S*)-4,6-dimethyl-5-((tert-butyldimethylsilyl)oxy)-2(E)-heptenoate 在 copper(I) bromide dimethylsulfide complex 、 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 3.0h， 生成 (4R,5S,6S)-4-(Hydroxy-diphenyl-silanyl)-6-isopropyl-5-methyl-tetrahydro-pyran-2-one
  参考文献：
  名称：

  Diastereoselective Heteroatom-Directed Conjugate Addition of Silylcuprate Reagents to Unsaturated Carbonyls. A Stereoselective Route to .beta.-Carbonyl Siloxanes1

  摘要：

  Directed conjugate addition of the silylcuprate reagent lithium bis[diphenyl(diethylamino)silyl]-cuprate ((Ph(2)(Et(2)N)Si)(2)CuLi) to unsaturated esters and ketones is reported. The stereochemical course of the reaction can be-controlled by the presence of an appropriately disposed internal Lewis basic functionality, affording the corresponding beta-hydroxysilyl carbonyls with good to excellent levels of diastereoselection (e.g., 3b --> 4b).

  DOI：

  10.1021/jo00095a007
• 作为产物：
  描述：

  6-异丙基-5-甲基-四氢-吡喃-2-酮 以 乙醚 为溶剂， 反应 2.5h， 生成 methyl (4R*,5S*)-4,6-dimethyl-5-((tert-butyldimethylsilyl)oxy)-2(E)-heptenoate
  参考文献：
  名称：

  Synthesis of the branched nine-carbon unit of the type A streptogramins and other antibiotics

  摘要：

  DOI：

  10.1021/jo00277a047

文献信息

• Rapid Access to Polyketide Scaffolds via Vinylogous Mukaiyama Aldol Reactions
  作者：Jorma Hassfeld、Mathias Christmann、Markus Kalesse

  DOI：10.1021/ol016677o

  日期：2001.11.1

  [reaction: see text]. The use of the Z-configured vinylogous silyl ketene acetals in Mukaiyama aldol reactions is described. Isopropyl alcohol as scavanger and the use of tris(pentafluorophenyl)borane as the Lewis acid are required for obtaining the gamma-alkylated syn-product selectively. In cases of alpha-chiral aldehydes, Felkin-Anh selectivity was observed.

  [反应：请参见文字]。描述了Z构型的乙烯基硅烷基乙烯酮缩醛在Mukaiyama羟醛反应中的用途。为了选择性地获得γ-烷基化的合成产物，需要异丙醇作为稀溶剂，并使用三（五氟苯基）硼烷作为路易斯酸。在α-手性醛的情况下，观察到Felkin-Anh选择性。
• KAZMIERCZAK, FRANCISZEK;HELQUIST, PAUL, J. ORG. CHEM., 54,(1989) N6, C. 3988-3992
  作者：KAZMIERCZAK, FRANCISZEK、HELQUIST, PAUL

  DOI：——

  日期：——
• Synthesis of the branched nine-carbon unit of the type A streptogramins and other antibiotics
  作者：Franciszek Kazmierczak、Paul Helquist

  DOI：10.1021/jo00277a047

  日期：1989.8
• Diastereoselective Heteroatom-Directed Conjugate Addition of Silylcuprate Reagents to Unsaturated Carbonyls. A Stereoselective Route to .beta.-Carbonyl Siloxanes1
  作者：Michael R. Hale、Amir H. Hoveyda

  DOI：10.1021/jo00095a007

  日期：1994.8

  Directed conjugate addition of the silylcuprate reagent lithium bis[diphenyl(diethylamino)silyl]-cuprate ((Ph(2)(Et(2)N)Si)(2)CuLi) to unsaturated esters and ketones is reported. The stereochemical course of the reaction can be-controlled by the presence of an appropriately disposed internal Lewis basic functionality, affording the corresponding beta-hydroxysilyl carbonyls with good to excellent levels of diastereoselection (e.g., 3b --> 4b).