methyl (E)-4-<(tert-butyldimethylsilyl)oxy>-3-methyl-2-butenoate | 95864-49-6

• 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 (E)-4-<(tert-butyldimethylsilyl)oxy>-3-methyl-2-butenoate
• 英文别名: (E)-methyl-1-(tert-butyldimethylsilyloxy)-2-methyl-4-butenoate；methyl (E)-4-((tert-butyldimethylsilyl)oxy)-3-methylbut-2-enoate；methyl (E)-4-[tert-butyl(dimethyl)silyl]oxy-3-methylbut-2-enoate
• CAS: 95864-49-6
• 化学式: C₁₂H₂₄O₃Si
• 分子量: 244.406
• InChiKey: HTJIGOGNVJJPBH-CSKARUKUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.13
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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 (E)-4-<(tert-butyldimethylsilyl)oxy>-3-methyl-2-butenoate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (E)-methyl 4-hydroxy-3-methylbut-2-enoate
  参考文献：
  名称：

  Bond-Weakening Catalysis: Conjugate Aminations Enabled by the Soft Homolysis of Strong N–H Bonds

  摘要：

  The ability of redox-active metal centers to weaken the bonds in associated ligands is well precedented, but has rarely been utilized as a mechanism of substrate activation in catalysis. Here we,describe a catalytic bond-weakening protocol for conjugate amination wherein the strong N-H bonds in N-aryl amides (N-H bond dissociation free energies similar to 100 kcal/mol) are destabilized by similar to 33 kcal/mol upon by coordination to a reducing titanocene complex, enabling their abstraction by the weak H-atom acceptor TEMPO through a proton-coupled electron transfer process. Significantly, this soft homolysis mechanism provides a method to generate closed-shell, metalated nucleophiles under neutral conditions in the absence of a Bronsted base.

  DOI：

  10.1021/jacs.5b03428
• 作为产物：
  描述：

  (E)-methyl 4-hydroxy-3-methylbut-2-enoate 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 生成 methyl (E)-4-<(tert-butyldimethylsilyl)oxy>-3-methyl-2-butenoate
  参考文献：
  名称：

  A synthesis of .beta.-methylene-.gamma.-butyrolactones.

  摘要：

  DOI：

  10.1021/jo00211a037

文献信息

• First Comprehensive Bakkane Approach:  Stereoselective and Efficient Dichloroketene-Based Total Syntheses of (±)- and (−)-9-Acetoxyfukinanolide, (±)- and (+)-Bakkenolide A, (−)-Bakkenolides III, B, C, H, L, V, and X, (±)- and (−)-Homogynolide A, (±)-Homogynolide B, and (±)-Palmosalide C
  作者：Timothy J. Brocksom、Fernando Coelho、Jean-Pierre Deprés、Andrew E. Greene、Marco E. Freire de Lima、Olivier Hamelin、Benoît Hartmann、Alice M. Kanazawa、Yanyun Wang

  DOI：10.1021/ja0208456

  日期：2002.12.1

  dichloroketene with dimethylcyclohexenes has been used as the key reaction in an efficient, general approach to the bakkanes. New methods and methodologies that have been developed in this work include spiro beta-methylene-gamma-butyrolactonizations, a vicinal dicarboxylation, an angelic ester preparation, a transesterification, an epoxy ketone double reduction, and a retro aldol-aldol approach to low-energy aldol

  二氯乙烯酮与二甲基环己烯的环加成反应已被用作一种有效、通用的巴卡内酯方法中的关键反应。在这项工作中开发的新方法和方法包括螺β-亚甲基-γ-丁内酯化、邻位二羧化、当归酯制备、酯交换、环氧酮双还原和低能量的逆羟醛-羟醛方法醛醇异构体。
• Enantiocontrolled total synthesis of (+)-bakkenolide-A
  作者：Andrew E. Greene、Fernando Coelho、Jean-Pierre Deprés、Timothy J. Brocksom

  DOI：10.1016/s0040-4039(00)80838-2

  日期：1988.1

  An efficient, stereoselective total synthesis of natural bakkenolide-A has been effected from (S)-1,6-dimethyl-1-cyclohexene, which can be obtained from 2-methyl-2-cyclohexen-1-one in 3 high-yield steps.

  从（S）-1,6-二甲基-1-环己烯可以有效地，立体选择性地合成天然巴克诺德内酯A，该化合物可从2-甲基-2-环己烯-1-酮中以3种高收率获得脚步。
• Stereoselective synthesis of (−)-homogynolide-A
  作者：Benoît Hartmann、Alice M. Kanazawa、Jean-Pierre Deprés、Andrew E. Greene

  DOI：10.1016/s0040-4039(00)79251-3

  日期：1993.6

  (-)-Homogynolide-A, a spiro beta-methylene-gamma-butyrolactone sesquiterpene from Homogyne alpina, has been stereoselectively prepared in natural form from S-(+)-carvone.

  (-)-霍莫金尼醇酯A，是一种从阿尔卑斯山霍莫金属植物中提取的螺式γ-丁内酯倍半萜烯，已经从S-(+)-欧薄荷脑中以立体选择性方式制备成天然形式。
• Synthesis of 2-<i>C</i>-Methyl-<scp>d</scp>-erythritol 4-Phosphate:  The First Pathway-Specific Intermediate in the Methylerythritol Phosphate Route to Isoprenoids
  作者：Andrew T. Koppisch、Brian S. J. Blagg、C. Dale Poulter

  DOI：10.1021/ol991299x

  日期：2000.1.1

  2-C-Methyl-D-erythritol 4-phosphate (4), formed from 1-deoxy-D-xylulose 5-phosphate (3), is the first pathway-specific intermediate in the methylerythritol phosphate route for the biosynthesis of isoprenoid compounds in bacteria, algae, and plant chloroplasts. In this report, 4 was synthesized from 1,2 propanediol (7) in seven steps with an overall yield of 32% and in an enantiomeric excess of 78%.
• An approach to the bakkanes. A short, stereocontrolled total synthesis of (.+-.)-bakkenolide A
  作者：Andrew E. Greene、Jean Pierre Depres、Fernando Coelho、Timothy J. Brocksom

  DOI：10.1021/jo00220a060

  日期：1985.10