(3R,5S)-1-ethynyl-3-hydroxy-2-methyl-5-[(vinyloxy)carbonyloxy]-1-cyclohexene | 250590-23-9

• 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: (3R,5S)-1-ethynyl-3-hydroxy-2-methyl-5-[(vinyloxy)carbonyloxy]-1-cyclohexene
• 英文别名: ethenyl [(1S,5R)-3-ethynyl-5-hydroxy-4-methylcyclohex-3-en-1-yl] carbonate
• CAS: 250590-23-9
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: LTFUMIMQLZYRTB-WDEREUQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3R,5S)-1-ethynyl-3-hydroxy-2-methyl-5-[(vinyloxy)carbonyloxy]-1-cyclohexene 在 肼 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 生成 (3R,5S)-5-(carbazoyloxy)-1-ethynyl-3-hydroxy-2-methyl-1-cyclohexene
  参考文献：
  名称：

  1α,25-Dihydroxyvitamin D₃ A-Ring Precursors:  Studies on Regioselective Enzymatic Alkoxycarbonylation Reactions of Their Stereoisomers. Chemoenzymatic Synthesis of A-Ring Synthon Carbamate Derivatives, Including Carbazates and Polyamino Carbamates

  摘要：

  The stereoisomers of 1 alpha,25-dihydroxyvitamin D-3 A-ring synthon 3a, named 3b-d, were subjected to a very comprehensive regioselective enzymatic study with Candida antarctica lipase (CAL). From this, it emerged that 3b, the enantiomer of the natural A-ring synthon, was a very goad substrate for CAL in toluene, dioxane, or THF, showing in all cases conversions close to 100% and regioselectivities between 95% and 99% toward the C-5-(S) hydroxyl group. The best results for the regioselective enzymatic transformation of stereoisomer 3c were achieved with toluene at 30 degrees C or with THF at 60 degrees C. The regioselectivity displayed a preference toward the C-5-(S) hydroxyl group. The 1:10 ratio (3c:4) was mandatory so as to obtain an acceptable degree of conversion (in dioxane or THF). The A-ring synthon 3d has a surprising conduct, suffering C-5-(R) enzymatic alkoxycarbonylation, whereas in the acylation process with Chromobacterium viscosum lipase, it showed behavior opposite to that observed for 3a-c. In addition to the above, an efficient chemoenzymatic synthesis of A-ring synthon carbamate derivatives 15a,c-17a,c, including carbazates 15b-17b, and polyamino carbamates 15d-17d was accomplished by a two-step strategy, involving the regioselective enzymatic synthesis of carbonates 5, 7, and 10, followed by reaction with (poly)amino derivatives 14.

  DOI：

  10.1021/jo990813+
• 作为产物：
  描述：

  (3R,5S)-1-ethynyl-3,5-dihydroxy-2-methylcyclohex-1-ene 在 吡啶 、 氢氧化钾 、 potassium dihydrogenphosphate 、 磷脂酶B 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 49.0h， 生成 (3R,5S)-1-ethynyl-3-hydroxy-2-methyl-5-[(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

• 1α,25-Dihydroxyvitamin D₃ A-Ring Precursors:  Studies on Regioselective Enzymatic Alkoxycarbonylation Reactions of Their Stereoisomers. Chemoenzymatic Synthesis of A-Ring Synthon Carbamate Derivatives, Including Carbazates and Polyamino Carbamates
  作者：Vicente Gotor-Fernández、Miguel Ferrero、Susana Fernández、Vicente Gotor

  DOI：10.1021/jo990813+

  日期：1999.10.1

  The stereoisomers of 1 alpha,25-dihydroxyvitamin D-3 A-ring synthon 3a, named 3b-d, were subjected to a very comprehensive regioselective enzymatic study with Candida antarctica lipase (CAL). From this, it emerged that 3b, the enantiomer of the natural A-ring synthon, was a very goad substrate for CAL in toluene, dioxane, or THF, showing in all cases conversions close to 100% and regioselectivities between 95% and 99% toward the C-5-(S) hydroxyl group. The best results for the regioselective enzymatic transformation of stereoisomer 3c were achieved with toluene at 30 degrees C or with THF at 60 degrees C. The regioselectivity displayed a preference toward the C-5-(S) hydroxyl group. The 1:10 ratio (3c:4) was mandatory so as to obtain an acceptable degree of conversion (in dioxane or THF). The A-ring synthon 3d has a surprising conduct, suffering C-5-(R) enzymatic alkoxycarbonylation, whereas in the acylation process with Chromobacterium viscosum lipase, it showed behavior opposite to that observed for 3a-c. In addition to the above, an efficient chemoenzymatic synthesis of A-ring synthon carbamate derivatives 15a,c-17a,c, including carbazates 15b-17b, and polyamino carbamates 15d-17d was accomplished by a two-step strategy, involving the regioselective enzymatic synthesis of carbonates 5, 7, and 10, followed by reaction with (poly)amino derivatives 14.
• Regioselective enzymatic syntheses of C-3 and C-5 carbonate A-ring stereoisomeric precursors of vitamin D
  作者：Daniel Oves、Vicente Gotor-Fernández、Susana Fernández、Miguel Ferrero、Vicente Gotor

  DOI：10.1016/j.tetasy.2004.07.052

  日期：2004.9

  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.