(-)-(6R,14R,12S,3E,9E)-6,14-dimethyl-12-hydroxy-1,7-dioxacyclotetradeca-3,9-diene-2,8-dione | 50376-40-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (-)-(6R,14R,12S,3E,9E)-6,14-dimethyl-12-hydroxy-1,7-dioxacyclotetradeca-3,9-diene-2,8-dione
• 英文别名: (-)-colletol；colletol；(3E,6R,9E,12S,14R)-12-hydroxy-6,14-dimethyl-1,7-dioxacyclotetradeca-3,9-diene-2,8-dione
• CAS: 50376-40-4
• 化学式: C₁₄H₂₀O₅
• 分子量: 268.31
• InChiKey: YWQZBDUTAGUPGW-VGAGTADTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  ethyl (R,E)-5-(tert-butyldimethylsilyloxy)hex-2-enoate 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex titanium(IV) isopropylate 、 盐酸 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 甲酸 、 草酰氯 、 三甲基溴硅烷 、 sodium hydride 、 二甲基亚砜 、 (-)-diethyl tartrate 、 1-chloro-3-hydroxy-1,1,3,3-tetrabutyldistannoxane 、 三乙胺 、 N,N-二异丙基乙胺 、 N,N'-二环己基碳二亚胺 、 三苯基膦 、 2,6-二氯苯甲酰氯 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 生成 (-)-(6R,14R,12S,3E,9E)-6,14-dimethyl-12-hydroxy-1,7-dioxacyclotetradeca-3,9-diene-2,8-dione
  参考文献：
  名称：

  基于钯催化甲酸还原裂解烯基环氧乙烷的 (-)-Colletol 手性合成

  摘要：

  (-)-colletol 的全合成是通过钯催化氢解旋光 (E)-4,5-epoxy-2-alkenoates 为 (E)-5-hydroxy-2-alkenoates 与甲酸作为关键步骤用于制备中间羟基酯链段。

  DOI：

  10.1246/cl.1993.1759

文献信息

• First ‘chiron approach’ based convergent synthesis of (−)-colletol from D-xylose
  作者：GVM Sharma、AVS Raja Rao、VS Murthy

  DOI：10.1016/0040-4039(95)96260-e

  日期：1995.6

  A protocol, based on ‘chiron approach’, for the synthesis of (−)-colletol is described, which involves the coupling of two appropriately protected hydroxy acids that are derived from D-xylose and macrolactonisation of seco-acid under Yamaguchi conditions.

  描述了一种基于'Chiron方法'的合成（-）-colletol的协议，该协议涉及将两个适当保护的衍生自D-木糖的羟基酸偶联，并在山口条件下将癸二酸进行大内酯化。
• Total synthesis of (-)-colletol
  作者：Gary E. Keck、Jerry A. Murry

  DOI：10.1021/jo00023a029

  日期：1991.11

  The first total synthesis of the unsymmetrical bis-macrolide (-)-colletol is described. The synthesis involves a Lewis acid mediated addition of triphenylallylstannane to aldehyde 14 to set the C12 stereochemistry. The penultimate step utilized macrolactonization to assemble the 14-membered ring. The natural product was prepared in 12 linear steps and 12% overall yield.
• Enantioselective Syntheses of Colletodiol, Colletol, and Grahamimycin A
  作者：Thomas J. Hunter、George A. O'Doherty

  DOI：10.1021/ol0269502

  日期：2002.12.1

  [GRAPHICS]The enantioselective synthesis of colletodiol has been achieved in 11 steps from methyl 1,3,5-octatrienoate and 16 total steps from both ethyl sorbate and methyl 1,3,5-octatrienoate. The route relies upon an enantio- and regioselective Sharpless dihydroxylation and a palladium-catalyzed reduction to form a 5-hydroxy-1-enoate and an 7-hydroxy-1,3-dienoate. These esters were further functionalized, coupled, and macrolactonized to provide colletodiol after deprotection. Grahamimycin A and colletol were synthesized in one and two steps, respectively, from colletodiol.
• Stereoselective Total Synthesis of (-)-Colletol by Prins Cyclisation
  作者：Jhillu Yadav、N. Reddy、P. Reddy、Hissana Ather、Attaluri Prasad

  DOI：10.1055/s-0029-1218679

  日期：2010.5

  A simple and efficient asymmetric total synthesis of the bis-macrolactone (-)-colletol was accomplished, proving the versatility of the Prins cyclisation in natural product synthesis. The synthesis mainly relies upon reductive opening of a pyran ring, Mitsunobu inversion, the Wittig reaction, and Yamaguchi macrolactonisation as the key steps.
• Enantioselective Synthesis of the Unsymmetrical Bis(lactone) (−)-(3E,6R,9E,12S,14R)-Colletol Induced by Chiral Sulfoxides and an Approach to (+)-Colletodiol by Asymmetric Hydroxylation of an α,β-Hydroxy Lactone
  作者：Guy Solladié、Laurence Gressot、Françoise Colobert

  DOI：10.1002/(sici)1099-0690(200001)2000:2<357::aid-ejoc357>3.0.co;2-n

  日期：2000.1

  A general synthetic strategy towards the two bis(lactones) (-)-colletol (1) and (+)-colletodiol (2) is described. A common intermediate in this synthesis is the 6-membered hydroxy lactone (+)-(3R,SR)-3-hydroxy-5-hexanolide (6), readily prepared by stereoselective reduction of (+)-(SR)-methyl 3,5-dioxo -6-(p-toluenesulfinyl)hexanoate (7). Stereoselective hydroxylation of this hydroxy lactone has allowed efficient access to (+)-colletodiol(2).