(2'S,3aS,4S,6aR)-2'-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethylspiro[3a,6a-dihydrofuro[3,4-d][1,3]dioxole-4,1'-cyclopentane]-6-one | 797801-27-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2'S,3aS,4S,6aR)-2'-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethylspiro[3a,6a-dihydrofuro[3,4-d][1,3]dioxole-4,1'-cyclopentane]-6-one
• CAS: 797801-27-5
• 化学式: C₁₇H₃₀O₅Si
• 分子量: 342.508
• InChiKey: IPFFGZALYWDRJN-PFHKOEEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.38
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2'S,3aS,4S,6aR)-2'-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethylspiro[3a,6a-dihydrofuro[3,4-d][1,3]dioxole-4,1'-cyclopentane]-6-one 在 吡啶 、 N,N-二甲基丙烯基脲 、 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 为溶剂， 反应 4.5h， 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：

  (5S,6S)-6-(tert-Butyl-dimethyl-silanyloxy)-1-oxa-spiro[4.4]non-3-en-2-one 在 ruthenium trichloride 、 sodium periodate 、 对甲苯磺酸 作用下， 以 乙酸乙酯 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 168.03h， 生成 (2'S,3aS,4S,6aR)-2'-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethylspiro[3a,6a-dihydrofuro[3,4-d][1,3]dioxole-4,1'-cyclopentane]-6-one
  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

文献信息

• Highly Stereoselective β-Anomeric Glycosidation of a 2‘-Deoxy <i>S</i><i>yn</i>-5‘-Configured 4‘-Spironucleoside
  作者：Shuzhi Dong、Leo A. Paquette

  DOI：10.1021/jo052324h

  日期：2006.2.1

  [GRAPHICS]A direct enantioselective pathway that delivers exclusively the beta-anomer of a 4'-spironucleoside has been successfully developed. The key starting material is the enantiomerically pure dihydroxy lactone 19, which has proven amenable to conversion to glycal 22 via the chloro acetonide. This intermediate is then capped as the 3,5-O-(tetraisopropyldisiloxane-1,3-diyl) glycal. The latter can enter into N-iodosuccinimide-promoted glycosidation with persilylated thymine. Only the beta anomer is formed. Ensuing deiodination and desilylation proceed quantitatively to furnish the targeted, previously elusive anomer.
• 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.