(3S,5R)-1-ethynyl-2-methyl-3,5-bis[(vinyloxy)carbonyloxy]-1-cyclohexene | 190264-67-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: (3S,5R)-1-ethynyl-2-methyl-3,5-bis[(vinyloxy)carbonyloxy]-1-cyclohexene
• 英文别名: [(1S,5R)-5-ethenoxycarbonyloxy-3-ethynyl-2-methylcyclohex-2-en-1-yl] ethenyl carbonate
• CAS: 190264-67-6
• 化学式: C₁₅H₁₆O₆
• 分子量: 292.288
• InChiKey: AJKXCTBINJQLDW-OLZOCXBDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (3S,5R)-1-ethynyl-2-methyl-3,5-bis[(vinyloxy)carbonyloxy]-1-cyclohexene 在 氢氧化钾 、 potassium dihydrogenphosphate 、 pig liver esterase 作用下， 以 1,4-二氧六环 为溶剂， 反应 25.0h， 生成 (3S,5R)-1-ethynyl-3,5-dihydroxy-2-methylcyclohex-1-ene
  参考文献：
  名称：

  Regioselective enzymatic syntheses of C-3 and C-5 carbonate A-ring stereoisomeric precursors of vitamin D

  摘要：

  The synthesis of selectively modified A-ring precursors for the preparation of 1alpha,25-dihydroxyvitamin D-3 analogues by enzymatic hydrolysis reaction of corresponding dicarbonates has been accomplished. Thus, Candida rugosa lipase (CRL) was found to hydrolyze with high selectivity the C-3 carbonate of stereoisomers 4a,b, and 4d, furnishing C-5 vinyloxycarbonates 5a,b, and 5d. On the other hand, Chromobacterium viscosum lipase exhibit opposite regioselectivity with cis enantiomers 4c and 4d, catalyzing hydrolysis at the C-5 carbonate for 4c and at C-3 position for 4d. In addition, CRL catalyzes the alkoxycarbonylation reaction at C-3 of diol 3d affording the monocarbonate complementary to the one obtained by the enzymatic hydrolysis process. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.07.052
• 作为产物：
  描述：

  氯甲酸乙烯酯 、 (3S,5R)-1-ethynyl-3,5-dihydroxy-2-methylcyclohex-1-ene 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以87%的产率得到(3S,5R)-1-ethynyl-2-methyl-3,5-bis[(vinyloxy)carbonyloxy]-1-cyclohexene
  参考文献：
  名称：

  Regioselective enzymatic syntheses of C-3 and C-5 carbonate A-ring stereoisomeric precursors of vitamin D

  摘要：

  The synthesis of selectively modified A-ring precursors for the preparation of 1alpha,25-dihydroxyvitamin D-3 analogues by enzymatic hydrolysis reaction of corresponding dicarbonates has been accomplished. Thus, Candida rugosa lipase (CRL) was found to hydrolyze with high selectivity the C-3 carbonate of stereoisomers 4a,b, and 4d, furnishing C-5 vinyloxycarbonates 5a,b, and 5d. On the other hand, Chromobacterium viscosum lipase exhibit opposite regioselectivity with cis enantiomers 4c and 4d, catalyzing hydrolysis at the C-5 carbonate for 4c and at C-3 position for 4d. In addition, CRL catalyzes the alkoxycarbonylation reaction at C-3 of diol 3d affording the monocarbonate complementary to the one obtained by the enzymatic hydrolysis process. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.07.052

文献信息

• Selective Alkoxycarbonylation of A-Ring Precursors of Vitamin D Using Enzymes in Organic Solvents. Chemoenzymatic Synthesis of 1α,25-Dihydroxyvitamin D₃ C-5 A-Ring Carbamate Derivatives¹
  作者：Miguel Ferrero、Susana Fernández、Vicente Gotor

  DOI：10.1021/jo970133b

  日期：1997.6.1

  of vitamin D-related structures. An efficient synthesis of 1alpha,25-(OH)(2)-D(3) C-5 A-ring carbamate derivatives 19 and amino acid derivatives 21 was developed by applying a two-step chemoenzymatic strategy, involving the enzymatic synthesis of carbonates followed by reaction with amino derivatives. Accordingly, we began the studies of enzymatic alkoxycarbonylation of 1alpha,25-(OH)(2)-D(3) A-ring

  A环修饰的1alpha，25-dihydroxyvitamin D（3）[2，1alpha，25-（OH）（2）-D（3）]是模拟研究的重要领域，以研究维生素D相关结构的生物活性。有效的合成1alpha，25-（OH）（2）-D（3）C-5 A环氨基甲酸酯衍生物19和氨基酸衍生物21通过应用两步化学酶催化策略，涉及碳酸盐的酶促合成然后与氨基衍生物反应。因此，我们开始了1α，25-（OH）（2）-D（3）A环前体7的酶法烷氧基羰基化的研究。发现南极假丝酵母脂肪酶（CAL）是甲苯中的最佳催化剂。区域选择性烷氧基羰基化仅在C-5-（R）羟基上发生。通过使这些碳酸盐与氨基衍生物进行化学反应，可以实现良好的优良收率。