6-methyl-6-(3-iodopropyl)-1,4,8,11-tetraoxadispiro[4.1.4.2]tridecane | 160146-76-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-methyl-6-(3-iodopropyl)-1,4,8,11-tetraoxadispiro[4.1.4.2]tridecane
• 英文别名: 6-(3-Iodopropyl)-6-methyl-1,4,8,11-tetraoxadispiro[4.1.47.25]tridecane
• CAS: 160146-76-9
• 化学式: C₁₃H₂₁IO₄
• 分子量: 368.212
• InChiKey: BIKJEBPMURYGGT-UHFFFAOYSA-N

物化性质

• 沸点：
  408.1±40.0 °C(Predicted)
• 密度：
  1.58±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  6-methyl-6-(3-iodopropyl)-1,4,8,11-tetraoxadispiro[4.1.4.2]tridecane 在 amberlyst-15 potassium tert-butylate 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醚 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 27.5h， 生成 [(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] (1R,7aS)-1-hydroxy-7a-methyl-1-prop-1-en-2-yl-3,5,6,7-tetrahydro-2H-indene-4-carboxylate
  参考文献：
  名称：

  A New Candidate for a Properly Substituted CD Ring Component of Vitamin D3 via Intramolecular Asymmetric Olefination of a 1,3-Cyclopentanedione Derivative

  摘要：

  A highly diastereoselective synthesis of hydrindenone derivative 5 (98% de) was achieved via diastereotopic differentiation of 1,3-cyclopentanedione derivative 4 by intramolecular Horner-Emmons olefination. In addition, the compound 5 was converted to ketone 2, a new building block far 1 alpha,25-dihydroxyvitamin D-3 (1).

  DOI：

  10.1021/jo00099a002
• 作为产物：
  描述：

  2-甲基-1,3-环戊二酮 在 palladium diacetate 、 三氟甲磺酸三甲基硅酯 、 三苯基膦 sodium hydroxide 、 dimethyl sulfide borane 、 双氧水 、 碳酸氢钠 、 三乙胺 、 sodium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 36.67h， 生成 6-methyl-6-(3-iodopropyl)-1,4,8,11-tetraoxadispiro[4.1.4.2]tridecane
  参考文献：
  名称：

  A New Candidate for a Properly Substituted CD Ring Component of Vitamin D3 via Intramolecular Asymmetric Olefination of a 1,3-Cyclopentanedione Derivative

  摘要：

  A highly diastereoselective synthesis of hydrindenone derivative 5 (98% de) was achieved via diastereotopic differentiation of 1,3-cyclopentanedione derivative 4 by intramolecular Horner-Emmons olefination. In addition, the compound 5 was converted to ketone 2, a new building block far 1 alpha,25-dihydroxyvitamin D-3 (1).

  DOI：

  10.1021/jo00099a002

文献信息

• Synthesis of Racemic and Enantiomerically Pure Acetylenic ω-Keto Esters Derived from 2-Methyl-1,3-cycloalkanediones and 2-Methylcycloalkanones Respectively
  作者：Michel Miesch、Philippe Geoffroy、Marie-Paule Ballet、Sidonie Finck、Eric Marchioni、Christophe Marcic

  DOI：10.1055/s-0029-1217043

  日期：2010.1

  Racemic and enantiomerically pure alkynyl esters tethered, respectively, to 2-methyl-1,3-cycloalkanediones and 2-methyl­cycloalkanones were readily obtained starting from common intermediates, which were available on large scale. alkynyl ester - enantiomer-chain - elongation - trimethylsilylpropyne - Corey-Fuchs reaction

  从常见的中间体开始容易地获得分别连接到2-甲基-1,3-环烷二酮和2-甲基环烷酮的外消旋和对映体纯的炔基酯，这些中间体可以大规模获得。 炔基酯-对映体链-伸长率-三甲基甲硅烷基丙炔-Corey-Fuchs反应
• Schinzer, Dieter; Blume, Thorsten; Jones, Peter G., Angewandte Chemie, 1996, vol. 108, # 21, p. 2669 - 2671
  作者：Schinzer, Dieter、Blume, Thorsten、Jones, Peter G.

  DOI：——

  日期：——
• Asymmetric construction of novel bicyclo[4.4.0] and [4.3.0]ring systems via intramolecular Horner–Wadsworth–Emmons reactions
  作者：Jiro Yamazaki、Ashutosh V. Bedekar、Toshiyuki Watanabe、Kiyoshi Tanaka、Joshu Watanabe、Kaoru Fuji

  DOI：10.1016/s0957-4166(02)00177-5

  日期：2002.5

  Novel perhydro-indanones and -naphthalenones having a quaternary stereogenic carbon and tetrasubstituted olefinic linkage were prepared via asymmetric intramolecular Horner-Wadsworth-Emmons reactions. The optically active binaphthyl phosphonates were connected with the 2-substituted cyclopenta- or cyclohexa-1,3-dione through the linker arm and the successive base treatment of the products with diethylzinc led to cyclization reactions with concomitant differentiation of diastereotopic carbonyl groups to afford the non-racemic title compounds in good enantiomeric excess. The absolute structure of the cyclized product was determined by X-ray analysis of its derived bromide. (C) 2002 Elsevier Science Ltd. All rights reserved.