(4R,5R)-1-<2,2-dimethyl-5-<(phenylmethoxy)methyl>-1,3-dioxolan-4-yl>ethanone | 171916-55-5

• 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: (4R,5R)-1-<2,2-dimethyl-5-<(phenylmethoxy)methyl>-1,3-dioxolan-4-yl>ethanone
• 英文别名: (3R,4S)-5-benzyloxy-3,4-isopropylidenedioxy-2-pentanone；1-[(4R,5S)-2,2-dimethyl-5-(phenylmethoxymethyl)-1,3-dioxolan-4-yl]ethanone
• CAS: 171916-55-5
• 化学式: C₁₅H₂₀O₄
• 分子量: 264.321
• InChiKey: IXSIHEHFLQDXJS-KBPBESRZSA-N

物化性质

• 沸点：
  364.9±42.0 °C(Predicted)
• 密度：
  1.078±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4R,5R)-1-<2,2-dimethyl-5-<(phenylmethoxy)methyl>-1,3-dioxolan-4-yl>ethanone 在 正丁基锂 、 copper(I) bromide dimethylsulfide complex 、 sodium hexamethyldisilazane 、 sodium hydride 、 二异丙胺 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 正己烷 、 甲苯 、 paraffin 为溶剂， 反应 43.92h， 生成 (1S,5R)-3,3,7,9,9-pentamethyl-5-<(phenylmethoxy)methyl>-2,4-dioxaspiro<4.4>non-6-ene
  参考文献：
  名称：

  Efficient Intramolecular C-H Insertion by an Alkylidene Carbene Generated from a Vinyl Chloride

  摘要：

  It is observed that chloride 4 on exposure to sodium bis(trimethylsilyl)amide smoothly generates the cyclopentene 5, by insertion of the intermediate alkylidene carbene into the methine C-H. Chloride 4 is prepared in several steps from L-tartaric acid. On ozonolysis and subsequent aldol condensation, 5 is transformed into 1, a synthon for the A ring of taxol 2.

  DOI：

  10.1021/jo00125a050
• 作为产物：
  描述：

  (4S,5R)-4-benzyloxymethyl-2,2-dimethyl-1,3-dioxolane-5-carboxaldehyde 在 sodium acetate 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 9.0h， 生成 (4R,5R)-1-<2,2-dimethyl-5-<(phenylmethoxy)methyl>-1,3-dioxolan-4-yl>ethanone
  参考文献：
  名称：

  Efficient Intramolecular C-H Insertion by an Alkylidene Carbene Generated from a Vinyl Chloride

  摘要：

  It is observed that chloride 4 on exposure to sodium bis(trimethylsilyl)amide smoothly generates the cyclopentene 5, by insertion of the intermediate alkylidene carbene into the methine C-H. Chloride 4 is prepared in several steps from L-tartaric acid. On ozonolysis and subsequent aldol condensation, 5 is transformed into 1, a synthon for the A ring of taxol 2.

  DOI：

  10.1021/jo00125a050

文献信息

• Synthesis of methyl ketones from terminal olefins using PdCl2/CrO3 system mimicking the Wacker process
  作者：Rodney A. Fernandes、Venkati Bethi

  DOI：10.1016/j.tet.2014.05.022

  日期：2014.8

  An efficient synthesis of methyl ketones from terminal olefins using PdCl2/CrO3 system mimicking the Wacker process is developed. The method shows good functional groups compatibility, no aldehyde by-products and is operationally simple. CrO3 is the sole oxidant and replaces both Cu-salts and molecular oxygen, traditionally used in this process. The method holds potential for future applications in

  开发了使用模仿Wacker工艺的PdCl 2 / CrO 3系统从末端烯烃高效合成甲基酮的方法。该方法显示出良好的官能团相容性，没有醛副产物，并且操作简单。CrO 3是唯一的氧化剂，可替代传统上在此过程中使用的铜盐和分子氧。该方法具有在有机合成中未来应用的潜力。
• Selectivity in the cycloadditions of carbonyl ylides with glyoxylates: an approach to the zaragozic acids—squalestatins
  作者：David M. Hodgson、James M. Bailey、Carolina Villalonga-Barber、Michael G. B. Drew、Timothy Harrison

  DOI：10.1039/b004870o

  日期：——

  Reaction of diazodiketoester 8 with glyoxylates in the presence of catalytic rhodium(II) acetate generates 6,8-dioxabicyclo[3.2.1]octanes 9 and 11 in good yield. Elaboration of 9 provides a suitable alcohol 25 for acid-catalysed rearrangement to give the 2,8-dioxabicyclo[3.2.1]octane skeleton 26 of the zaragozic acids—squalestatins. More substituted diazodiketoesters 36 and 40 also undergo highly regio- and diastereoselective cycloaddition with glyoxylates to give the cycloadducts 41, 43 and 44.

  在催化量的醋酸铑(II)存在下，二氮二酮酯8与甘油二酸酯反应，以良好产率生成6,8-二氧双环[3.2.1]辛烷9和11。对9的进一步修饰提供了适合的醇25，通过酸催化重排可得到2,8-二氧双环[3.2.1]辛烷骨架26，这是扎戈西酸——角鲨烷抑制剂的结构部分。更多取代的二氮二酮酯36和40也能与甘油二酸酯发生高度区域选择性和立体选择性的环加成反应，生成环加成产物41、43和44。
• Efficient Intramolecular C-H Insertion by an Alkylidene Carbene Generated from a Vinyl Chloride
  作者：Douglass F. Taber、Ayman Sahli、Han Yu、Robert P. Meagley

  DOI：10.1021/jo00125a050

  日期：1995.10

  It is observed that chloride 4 on exposure to sodium bis(trimethylsilyl)amide smoothly generates the cyclopentene 5, by insertion of the intermediate alkylidene carbene into the methine C-H. Chloride 4 is prepared in several steps from L-tartaric acid. On ozonolysis and subsequent aldol condensation, 5 is transformed into 1, a synthon for the A ring of taxol 2.