(4R,5R)-4-allyl-5-(hydroxymethyl)-2,2-dimethyl-1,3-dioxane | 140479-53-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,5R)-4-allyl-5-(hydroxymethyl)-2,2-dimethyl-1,3-dioxane
• 英文别名: [(4R,5R)-2,2-dimethyl-4-prop-2-enyl-1,3-dioxan-5-yl]methanol
• CAS: 140479-53-4
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: CCZSZECWBKZZRU-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.32
• 重原子数：
  13.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (4R,5R)-4-allyl-5-(hydroxymethyl)-2,2-dimethyl-1,3-dioxane 、 叔丁基二苯基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 以82%的产率得到(4R,5S)-cis-4-allyl-5-(((tert-butyldiphenylsilyl)oxy)methyl)-2,2-dimethyl-1,3-dioxane
  参考文献：
  名称：

  Synthesis of both top and bottom fragments of (-)-talaromycin A through enantiospecific and diastereoselective elaboration of asymmetrized tris (hydroxymethyl)methane

  摘要：

  Asymmetrized tria(hydroxymethyl)methane equivalents of general formula 5 have been employed as chiral building blocks for the enantiospecific and diastereoselective synthesis of both fragments 3 and 4, whose conversion into Talaromycin A was already reported. Preparation of bottom half fragment 3 was achieved through a ''protecting group-controlled'' stereoselective allylation of an asymmetrized bis(hydroxymethyl)acetaldehyde with allyltributyltin, while the top half fragment 4 was obtained in high overall yield by sequential elongation of two of the three synthetically equivalent masked hydroxymethyl group of 5, via nucleophilic substitution reactions.

  DOI：

  10.1021/jo00058a036
• 作为产物：
  描述：

  (2R,3R)-2-(4-Methoxy-benzyloxymethoxymethyl)-1-triisopropylsilanyloxy-hex-5-en-3-ol 在 dipotassium hydrogenphosphate 、 potassium dihydrogenphosphate 、 四丁基氟化铵 、 对甲苯磺酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 叔丁醇 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 12.17h， 生成 (4R,5R)-4-allyl-5-(hydroxymethyl)-2,2-dimethyl-1,3-dioxane
  参考文献：
  名称：

  Synthesis of both top and bottom fragments of (-)-talaromycin A through enantiospecific and diastereoselective elaboration of asymmetrized tris (hydroxymethyl)methane

  摘要：

  Asymmetrized tria(hydroxymethyl)methane equivalents of general formula 5 have been employed as chiral building blocks for the enantiospecific and diastereoselective synthesis of both fragments 3 and 4, whose conversion into Talaromycin A was already reported. Preparation of bottom half fragment 3 was achieved through a ''protecting group-controlled'' stereoselective allylation of an asymmetrized bis(hydroxymethyl)acetaldehyde with allyltributyltin, while the top half fragment 4 was obtained in high overall yield by sequential elongation of two of the three synthetically equivalent masked hydroxymethyl group of 5, via nucleophilic substitution reactions.

  DOI：

  10.1021/jo00058a036

文献信息

• Protecting group controlled diastereoselective allylation of asymmetrized bis (hydroxymethyl)acetaldehydes (BHYMA*)
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano

  DOI：10.1016/0040-4039(91)80449-g

  日期：1991.11

  MgBr2 catalysed allylation of a series of diprotected asymmetrized bis (hydroxymethyl)acetaldehydes 2 with allyltributylstannane proceeds with good diastereoselectivity. The stereochemical results are in line with a cyclic chelated transition state, where only one of the two CH2OR appendages, due to the different nature of protecting groups, is capable of coordinating the Lewis acid.