(3R,5R)-5-acetoxy-1-ethynyl-3-hydroxy-2-methylcyclohex-1-ene | 405197-18-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (3R,5R)-5-acetoxy-1-ethynyl-3-hydroxy-2-methylcyclohex-1-ene
• 英文别名: [(1R,5R)-3-ethynyl-5-hydroxy-4-methylcyclohex-3-en-1-yl] acetate
• CAS: 405197-18-4
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: AEQAHUJUJFRGQZ-GHMZBOCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R,5R)-5-acetoxy-1-ethynyl-3-hydroxy-2-methylcyclohex-1-ene 在 Lindlar's catalyst 咪唑 、 喹啉 、 copper(l) iodide 、 bis(triphenylphosphine) palladium (Il) acetate 、 四丁基氟化铵 、 氢气 、 碳酸氢钠 、 二乙胺 、 三苯基膦 、 甲胺 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 氯仿 、 水 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 84.83h， 生成 1α-[(tert-butoxycarbonyl)amino]-25-hydroxyvitamin D₃
  参考文献：
  名称：

  Efficient Synthesis of Novel 1α-Amino and 3β-Amino Analogues of 1α,25-Dihydroxyvitamin D₃

  摘要：

  Convenient synthetic routes to 1alpha-amino-25-hydroxyvitamin D-3 (3) and 3beta-amino-3-deoxy-1alpha,25-dihy-droxyvitamin D-3 (4), novel analogues of vitamin D-3 bearing an amino group at the C-1 or C-3 position, have been developed starting from (S)-(+)-carvone. Construction of the A-ring fragments was accomplished by selective enzymatic hydrolysis of a diester intermediate and introduction of the amino group under Mitsunobu conditions.

  DOI：

  10.1021/jo026474t
• 作为产物：
  描述：

  (1S,5R)-5-acetoxy-1-ethynyl-3-hydroxy-2-methylcyclohex-1-ene 在 potassium dihydrogenphosphate 、 Chromobacterium Viscosum lipase 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 水 为溶剂， 反应 6.5h， 生成 (3R,5R)-5-acetoxy-1-ethynyl-3-hydroxy-2-methylcyclohex-1-ene
  参考文献：
  名称：

  Efficient Synthesis of Novel 1α-Amino and 3β-Amino Analogues of 1α,25-Dihydroxyvitamin D₃

  摘要：

  Convenient synthetic routes to 1alpha-amino-25-hydroxyvitamin D-3 (3) and 3beta-amino-3-deoxy-1alpha,25-dihy-droxyvitamin D-3 (4), novel analogues of vitamin D-3 bearing an amino group at the C-1 or C-3 position, have been developed starting from (S)-(+)-carvone. Construction of the A-ring fragments was accomplished by selective enzymatic hydrolysis of a diester intermediate and introduction of the amino group under Mitsunobu conditions.

  DOI：

  10.1021/jo026474t

文献信息

• Selective Acylation of A-Ring Precursors of Vitamin D Using Enzymes in Organic Solvents
  作者：Susana Fernandez、b Miguel Ferrero、Vicente Gotor、William H. Okamura

  DOI：10.1021/jo00124a014

  日期：1995.9

  Whereas Chromobacterium viscosum lipase (CVL) catalyzes selectively the acylation of the C-5 hydroxyl of the three stereoisomeric vitamin D A-ring precursors 2a, 3a and 3b, only the C-3 hydroxyl of the fourth stereoisomer 2b is acylated under the same conditions in organic solvent. In a convenient application, the racemic vitamin D A-ring precursor 4, possessing only the C-5 hydroxyl, was resolved using suitable conditions identified from the studies of 2 and 3.
• Synthesis of Monoacyl A-Ring Precursors of 1α,25-Dihydroxyvitamin D₃ through Selective Enzymatic Hydrolysis
  作者：Vicente Gotor-Fernández、Miguel Ferrero、Susana Fernández、Vicente Gotor

  DOI：10.1021/jo010941+

  日期：2002.2.1

  An efficient synthesis of monoacylated 1alpha,25-dihydroxyvitamin D-3 A-ring precursors 15, 16, 18, and 19 has been described through an enzymatic hydrolysis process. Candida antarctica A lipase (CAL-A) hydrolyzes the C-5 acetate ester in trans stereoisomers 9 and 13, with complete and high selectivity, respectively. In the case of cis isomers 11 and 14, Chromobacterium viscosum lipase (CVL) is the enzyme of choice, exhibiting opposite selectivity for these two enantiomers. This lipase selectively catalyzes the hydrolysis at the C-3 acetate in diester 11 and at C-5 position in diester 14. It is noteworthy that through a hydrolysis reaction CAL-A and CVL allow the synthesis of the four A-ring monoacetylated precursors of 1alpha,25-dihydroxyvitamin D3, precursors which are complementary to those obtained by the enzymatic acylation process. In addition, with excellent yield CVL selectively hydrolyzes the C-3 chloroacetate ester instead of the C-5 acetate in diester 22, a key intermediate in the synthesis of new A-ring modified 1alpha,25-dihydroxyvitamin D3 analogues.