de-A,B-25-cholesten-8-one | 83076-51-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: de-A,B-25-cholesten-8-one
• 英文别名: (1R,3aR,7aR)-7a-methyl-1-[(2R)-6-methylhept-6-en-2-yl]-2,3,3a,5,6,7-hexahydro-1H-inden-4-one
• CAS: 83076-51-1
• 化学式: C₁₈H₃₀O
• 分子量: 262.436
• InChiKey: ADNIEJULDBPDCG-XLMAVXFVSA-N

物化性质

• 沸点：
  346.8±11.0 °C(Predicted)
• 密度：
  0.932±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.15
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  de-A,B-25-cholesten-8-one 生成 (1R,3aR)-7a-methyl-1-[(2R)-6-methylhept-6-en-2-yl]-2,3,3a,7-tetrahydro-1H-inden-4-one
  参考文献：
  名称：

  GIBBS, RICHARD A.;OKAMURA, WILLIIAM H., TETRAHEDRON LETT., 28,(1987) N 48, 6021-6024

  摘要：

  DOI：
• 作为产物：
  描述：

  (S)-2-((3R,3aR,7S,7aR)-octahydro-7-hydroxy-3a-methyl-1H-inden-3-yl)propyl 4-methylbenzenesulfonate 在 重铬酸吡啶 、 dilithium tetrachlorocuprate 、 三氟乙酸吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 14.5h， 生成 de-A,B-25-cholesten-8-one
  参考文献：
  名称：

  Studies of vitamin D (calciferol) and its analogs. 34. Potential inhibitors of vitamin D metabolism: an oxa analog of vitamin D

  摘要：

  DOI：

  10.1021/jo00243a035

文献信息

• Synthesis of 3-deoxy-1α,25-dihydroxy-9,11-dehydrovitamin D3: Selective formation of 6β-vitamin D vinylallenes and their thermal [1,5]-sigmatropic hydrogen shift
  作者：Richard A. Gibbs、William H. Okamura

  DOI：10.1016/s0040-4039(00)96853-9

  日期：1987.1

  also incapable of undergoing a [1,7]-sigmatropic hydrogen shift, was prepared in eight steps from the ketone 6. A stereoselective method for the preparation of 6β-vitamin D type vinylallenes was developed in this synthesis, starting from propargyl benzoate 10.

  从酮6到八步制备了CD环不饱和维生素4，它是一个具有扰动的π系统并且不能进行[1,7]-σ氢转移的类似物。从苯甲酸炔丙基酯10开始，开发了一种立体选择性的方法来制备6β-维生素D型乙烯基丙二烯。
• Studies of vitamin D (calciferol) and its analogs. 35. Synthesis and biological activity of 9,11-dehydrovitamin D3 analogs: stereoselective preparation of 6.beta.-vitamin D vinylallenes and a concise enynol synthesis for preparing the A-ring
  作者：William H. Okamura、J. Miguel Aurrecoechea、Richard A. Gibbs、Anthony W. Norman

  DOI：10.1021/jo00278a018

  日期：1989.8
• Studies on vitamin D (calciferol) and its analogs. 23. Effect of 3-methyl substituents on the thermal [1,5]- and [1,7]-sigmatropic hydrogen shifts of vinylallenes and other seco steroids related to vitamin D: synthesis of 3-methyl- and 3,3-dimethyl-substituted analogs of 3-deoxy-1.alpha.,25-dihydroxyvitamin D3
  作者：Gregory A. Leyes、William H. Okamura

  DOI：10.1021/ja00386a042

  日期：1982.11
• Vitamin D (calciferol) and its analogs. 40. 1.alpha.,25-Dihydroxyprevitamin D3: synthesis of the 9,14,19,19,19-pentadeuterio derivative and a kinetic study of its [1,7]-sigmatropic shift to 1.alpha.,25-dihydroxyvitamin D3
  作者：Michael L. Curtin、William H. Okamura

  DOI：10.1021/ja00018a038

  日期：1991.8

  The hormonally active steroid 1-alpha, 25-dihydroxyvitamin D3 (3) exists in equilibrium with its previtamin form 5. In an attempt to further understand the significance of this previtamin and previtamin D's in general, the pentadeuterio analogue of 5 was synthesized. Accordingly, 9, 14, 19, 19, 19-pentadeuterio-1-alpha, 25-dihydroxyprevitamin D3 (6) was prepared from the readily available, optically active synthons (S)-(+)-carvone (10) and the Inhoffen-Lythgoe diol (9). A general method was developed to regioselectively deuteriate beta-methyl-alpha,beta-unsaturated aldehydes via their Schiff bases and was used in the synthesis to convert aldehyde 16a to its deuteriated analogue 16b. Thermolysis of 6 afforded 9, 9, 14, 19, 19-pentadeuterio-1-alpha,25-dihydroxyvitamin D3 (24). A kinetic investigation of the [1, 7]-sigmatropic hydrogen (deuterium) shifts which convert previtams 5 and 6 to vitamins 3 and 24, respectively, revealed that at 25-degrees-C the process proceeds with a relatively normal primary kinetic isotope effect, k(H)/k(D), of 5.5.
• OKAMURA, WILLIAM H.;AURRECOECHEA, J. MIGUEL;GIBBS, RICHARD A.;NORMAN, ANT+, J. ORG. CHEM., 54,(1989) N7, C. 4072-4083
  作者：OKAMURA, WILLIAM H.、AURRECOECHEA, J. MIGUEL、GIBBS, RICHARD A.、NORMAN, ANT+

  DOI：——

  日期：——