(+)-(3S,4R,5S)-(2E)-3,4-epoxy-(2,4)-hexadiynyliden-1,6-dioxaspiro<4,5>decane | 69905-02-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-(3S,4R,5S)-(2E)-3,4-epoxy-(2,4)-hexadiynyliden-1,6-dioxaspiro<4,5>decane
• 英文别名: (2E,3S,4R,5S)-3,4-epoxy-2-(2,4-hexadiynylidene)-1,6-dioxaspiro[4.5]decane；C₅-epi-AL-2；(+)-(3S,4R,5S)-(2E)-3,4-epoxy-(2,4)-hexadiynyliden-1,6-dioxaspiro[4,5]decane
• CAS: 69905-02-8；116258-25-4；116258-26-5
• 化学式: C₁₄H₁₄O₃
• 分子量: 230.263
• InChiKey: HXGWJMJKRSKLGG-ABDLLDAISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.59
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  30.99
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (+)-(3S,4R,5S)-(2E)-3,4-epoxy-(2,4)-hexadiynyliden-1,6-dioxaspiro<4,5>decane 在 lithium aluminium tetrahydride 作用下， 生成 (4R,5S)-2-Hexa-2,4-diyn-(E)-ylidene-1,6-dioxa-spiro[4.5]decan-4-ol
  参考文献：
  名称：

  两种天然炔属螺环酮烯醇醚环氧化物的相对和绝对构型

  摘要：

  雪蒿的地下部分提供了一个新的C 14炔六环螺环酮烯醇醚环氧化物。一个密切相关的非对映体化合物先前已经分离，但是，环氧环（的相对构型反或顺式与参考氧气）不能成立。通过1 H-镧系元素引起的位移和13 C NMR数据的比较，阐明了反Syn对的相对立体化学。使用Horeau的方法通过相应的甲醇推导出绝对构型。结果用CD测量和平衡实验证实抗⇌顺式对。

  DOI：

  10.1016/s0040-4020(01)85117-6
• 作为产物：
  描述：

  (-)-(2E,3S,4R,5R)-3,4-epoxy-2-(2,4-hexadiynylidene)-1,6-dioxaspiro[4.5]decane 在 对甲苯磺酸 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 6.0h， 以14.6%的产率得到(+)-(3S,4R,5S)-(2E)-3,4-epoxy-(2,4)-hexadiynyliden-1,6-dioxaspiro<4,5>decane
  参考文献：
  名称：

  Isolation and Identification of Acetylenic Spiroketal Enol Ethers from Artemisia lactiflora as Inhibitors of Superoxide Generation Induced by a Tumor Promoter in Differentiated HL-60 Cells

  摘要：

  Six acetylenic compounds were isolated from the leaves of Artemisia lactiflora (Compositae), an edible plant of Thailand. Four of them were identified as the stereoisomers of 3,4-epoxy-2-(2,4-hexadiynylidene)-1,6-dioxaspiro[4.5]decane and its derivatives, whose planar structures have already been reported. The other two were identified as novel chlorohydrin derivatives of the corresponding diacetylene spiroketal enol ethers. The inhibitory effects of the polyacetylenes isolated in the present study together with genistein on TPA-induced O-2(-) generation were examined. It was revealed that an acyloxyl group at the C-2 position enhanced-the inhibitory effect, while the absolute configurations at C-5, -6, and -7 were not important. While polyacetylenes are known to possess several biological roles in various ecosystems, we first found inhibitory effects of the diacetylenes on TPA-induced O-2(-) generation in differentiated HL-60 cells.

  DOI：

  10.1021/jf980521u

文献信息

• Total Syntheses of Naturally Occurring Diacetylenic Spiroacetal Enol Ethers
  作者：Naoki Miyakoshi、Daisuke Aburano、Chisato Mukai

  DOI：10.1021/jo050822k

  日期：2005.7.1

  A highly stereoselective method for constructing a (2E)-methoxymethylidene-1,6-dioxaspiro[4.5]decane skeleton has been developed on the basis of the palladium(II)-catalyzed ring-closing reaction of the 3,4-dioxygenated-9-hydroxy-1-nonyn-5-one derivatives as a crucial step. The newly developed procedures could be successfully applied to the first total synthesis of five diacetylenic spiroacetal enol

  基于钯（II）催化的3,4-二加氧-环己基的闭环反应，开发了一种高度立体选择性的构建（2 E）-甲氧基亚甲基-1,6-dioxaspiro [4.5]癸烷骨架的方法。 9-羟基-1-nonyn-5-one衍生物是至关重要的步骤。新开发的程序可以成功地用于从酒石酸（R，R）-或（S，S）-二乙基酒石酸酯开始的五种二乙炔基螺缩醛烯醇醚天然产物的首次全合成。
• The absolute configuration determination of naturally occurring diacetylenic spiroacetal enol ethers from Artemisia lactiflora
  作者：Liang Ma、Fan Ge、Chun-Ping Tang、Chang-Qiang Ke、Xi-Qiang Li、Andreas Althammer、Yang Ye

  DOI：10.1016/j.tet.2011.03.022

  日期：2011.5

  Six new naturally occurring diacetylenic spiroacetal enol ethers, Lactiflodiynes A–F (1–6), together with five known congeners (7–11), were isolated from the whole plant of Artemisia lactiflora (Compositae). The structures were elucidated by extensive spectroscopic methods, X-ray crystallography, chemical transformations, and CD. The absolute configuration of Lactiflodiyne A (1) was determined to be

  六个新的天然存在的二乙炔螺缩醛烯醇醚，Lactiflodiynes A-F（1 - 6）中，用5个已知同系物（共7 - 11）中，从全植物分离角菜（菊）。通过广泛的光谱学方法，X射线晶体学，化学转化和CD阐明了结构。Lactiflodiyne A（1）的绝对构型确定为2 R，5 S，6 S和7 R通过MoKα辐射的X射线晶体衍射实验，绝对参数为0.01（8）。与CD组合，化合物的绝对构型2 - 11通过使用化学转化确认1作为起始原料。