(5S,6S)-6-(tert-Butyl-dimethyl-silanyloxy)-1-oxa-spiro[4.4]non-3-en-2-one | 341032-38-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: (5S,6S)-6-(tert-Butyl-dimethyl-silanyloxy)-1-oxa-spiro[4.4]non-3-en-2-one
• 英文别名: (5S,9S)-9-[tert-butyl(dimethyl)silyl]oxy-1-oxaspiro[4.4]non-3-en-2-one
• CAS: 341032-38-0
• 化学式: C₁₄H₂₄O₃Si
• 分子量: 268.428
• InChiKey: YRAQDNSUNKZDJX-FZMZJTMJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.41
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (5S,6S)-6-(tert-Butyl-dimethyl-silanyloxy)-1-oxa-spiro[4.4]non-3-en-2-one 在 吡啶 、 六甲基磷酰三胺 、 ruthenium trichloride 、 sodium periodate 、 三甲基氯硅烷 、 samarium diiodide 、 四氯化锡 、 二异丁基氢化铝 、 乙二醇 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 乙酸乙酯 、 乙腈 为溶剂， 反应 5.53h， 生成 1-[(2S,4S,5R,9S)-4,9-bis[[tert-butyl(dimethyl)silyl]oxy]-1-oxaspiro[4.4]nonan-2-yl]-5-methylpyrimidine-2,4-dione
  参考文献：
  名称：

  Stereochemical Features of Lewis Acid-Promoted Glycosidations Involving 4‘-Spiroannulated DNA Building Blocks

  摘要：

  Tin tetrachloride-catalyzed glycosidation of persilylated nucleobases with acetate donor 6 in CH2Cl2 solution followed by deprotection gave rise very predominantly to alpha-spironucleosides. These stereochemical assignments stem from the determination of NOE interactions and an X-ray crystallographic analysis of the latter product. Computational studies revealed that these results are consistent with the fact that the C5' substituent shields the beta-face of the oxonium ion involved in the coupling reaction while the C3' substituent is projected away from the alpha-underside. Attack from the more open direction is therefore kinetically favored. Entirely comparable calculations suggested that donor 19 should behave comparably. Experimentation involving this donor gave results consistent with this model although more equitable alpha/beta spironucleoside product ratios were seen when acetonitrile was employed as the reaction medium.

  DOI：

  10.1021/jo048904g
• 作为产物：
  描述：

  1-(4,5-dihydro-6-furyl)cyclobutanol 在 咪唑 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 lithium hydroxide 、 sodium periodate 、 amberlyst-15 、 L-Selectride 、 lithium hexamethyldisilazane 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 10.0h， 生成 (5S,6S)-6-(tert-Butyl-dimethyl-silanyloxy)-1-oxa-spiro[4.4]non-3-en-2-one
  参考文献：
  名称：

  1-Oxaspiro [4.4] nonan-6-ones。通过氧鎓离子技术，光学分辨率和转化为对映体纯的螺环α，β-丁烯内酯的合成途径。

  摘要：

  提出了合成对映体纯的螺环α，β-丁烯内酯的一般方法，其中基本构架通过酸或溴离子诱导的甲醇的重排反应而迅速完善，该重排反应是通过向2-硫代-4,5-二氢呋喃中添加而得到的。环丁酮。通过硫代亚胺或扁桃酸缩醛技术对所得酮的后续拆分已得到有效应用。这些结构单元的可获得性又使得获得以17、35和38为代表的二氢呋喃的对映异构体以及诸如25和31的内酯以及目标标题化合物成为可能。早期中间体的互补还原提供了额外的优势，即可以按需获得α-和β-立体异构甲醇系列。

  DOI：

  10.1021/jo010026o

文献信息

• 1-Oxaspiro[4.4]nonan-6-ones. Synthetic Access via Oxonium Ion Technology, Optical Resolution, and Conversion into Enantiopure Spirocyclic α,β-Butenolides
  作者：Leo A. Paquette、Dafydd R. Owen、Richard Todd Bibart、Christopher K. Seekamp、Alexandra L. Kahane、James C. Lanter、Miriam Alvarez Corral

  DOI：10.1021/jo010026o

  日期：2001.4.1

  A general approach to the synthesis of enantiomerically pure spirocyclic alpha,beta-butenolides is presented where the fundamental framework is rapidly elaborated by acid- or bromonium ion-induced rearrangement of the carbinol derived by addition of 2-lithio-4,5-dihydrofuran to cyclobutanone. Subsequent resolution of the resulting ketones by either sulfoximine or mandelate acetal technology has been

  提出了合成对映体纯的螺环α，β-丁烯内酯的一般方法，其中基本构架通过酸或溴离子诱导的甲醇的重排反应而迅速完善，该重排反应是通过向2-硫代-4,5-二氢呋喃中添加而得到的。环丁酮。通过硫代亚胺或扁桃酸缩醛技术对所得酮的后续拆分已得到有效应用。这些结构单元的可获得性又使得获得以17、35和38为代表的二氢呋喃的对映异构体以及诸如25和31的内酯以及目标标题化合物成为可能。早期中间体的互补还原提供了额外的优势，即可以按需获得α-和β-立体异构甲醇系列。
• Stereochemical Features of Lewis Acid-Promoted Glycosidations Involving 4‘-Spiroannulated DNA Building Blocks
  作者：Leo A. Paquette、Christopher K. Seekamp、Alexandra L. Kahane、David G. Hilmey、Judith Gallucci

  DOI：10.1021/jo048904g

  日期：2004.10.1

  Tin tetrachloride-catalyzed glycosidation of persilylated nucleobases with acetate donor 6 in CH2Cl2 solution followed by deprotection gave rise very predominantly to alpha-spironucleosides. These stereochemical assignments stem from the determination of NOE interactions and an X-ray crystallographic analysis of the latter product. Computational studies revealed that these results are consistent with the fact that the C5' substituent shields the beta-face of the oxonium ion involved in the coupling reaction while the C3' substituent is projected away from the alpha-underside. Attack from the more open direction is therefore kinetically favored. Entirely comparable calculations suggested that donor 19 should behave comparably. Experimentation involving this donor gave results consistent with this model although more equitable alpha/beta spironucleoside product ratios were seen when acetonitrile was employed as the reaction medium.