(+/-)-7-tert-butoxycarbonyl-5,6-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]hept-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (+/-)-7-tert-butoxycarbonyl-5,6-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]hept-2-one
• 英文别名: tert-butyl (1R,2R,6S,7R)-4,4-dimethyl-8-oxo-3,5-dioxa-10-azatricyclo[5.2.1.02,6]decane-10-carboxylate
• 化学式: C₁₄H₂₁NO₅
• 分子量: 283.324
• InChiKey: PYUPAUDGIRAIDL-DQDDRIPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+/-)-7-tert-butoxycarbonyl-5,6-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]hept-2-one 在 dimethyl sulfide borane 、 磷酸 、 4 A molecular sieve 、 臭氧 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 32.92h， 生成 (3aR,4R,6S,6aS)-tert-butyl 4,6-bis(hydroxymethyl)-2,2-dimethyl-6,6a-dihydro-3aH-[1,3]dioxolo[4,5-c]pyrrole-5(4H)-carboxylate
  参考文献：
  名称：

  Synthesis of d- and l-2,3-trans-3,4-cis-4,5-trans-3,4-Dihydroxy-5-hydroxymethylproline and Tripeptides Containing Them

  摘要：

  Enantiomerically pure (-)-(1R,4R,5R,6S)- and (+)-(1S,4S,5S,6R)-7-(tert-butoxycarbonyl)-5,6-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]hept-2-one ((-)-3 and (+)-3) have been obtained from the Diels-Alder adduct of N-(tert-butoxycarbonyl)pyrrole and 2-bromo-1-(p-toluenesulfonyl)acetylene, including the Alexakis optical resolution of ketone ()-3 via formation of cyclic aminals with (1R,2R)diphenylethylenediamine. Compounds (-)-3 and (+)-3 were converted into D- and L-2,3-trans-3,4-cis-4,5-trans-N-(tert-butoxycarbonyl)-5-hydroxymethyl-3,4-isopropylidenedioxyprolines (-)-4 and (+)4, respectively. Applying the Boc and Fmoc strategies of peptide synthesis, these compounds were used to construct two tripeptides containing the D- or L-2,3-trans-3,4-cis-4,5-trans-3,4-dihydroxy-5-hydroxymethylproline.

  DOI：

  10.1021/jo049637h
• 作为产物：
  描述：

  7-tert-butoxycarbonyl-5,6-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]heptan-2-endo-ol 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以91%的产率得到(+/-)-7-tert-butoxycarbonyl-5,6-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]hept-2-one
  参考文献：
  名称：

  Synthesis of d- and l-2,3-trans-3,4-cis-4,5-trans-3,4-Dihydroxy-5-hydroxymethylproline and Tripeptides Containing Them

  摘要：

  Enantiomerically pure (-)-(1R,4R,5R,6S)- and (+)-(1S,4S,5S,6R)-7-(tert-butoxycarbonyl)-5,6-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]hept-2-one ((-)-3 and (+)-3) have been obtained from the Diels-Alder adduct of N-(tert-butoxycarbonyl)pyrrole and 2-bromo-1-(p-toluenesulfonyl)acetylene, including the Alexakis optical resolution of ketone ()-3 via formation of cyclic aminals with (1R,2R)diphenylethylenediamine. Compounds (-)-3 and (+)-3 were converted into D- and L-2,3-trans-3,4-cis-4,5-trans-N-(tert-butoxycarbonyl)-5-hydroxymethyl-3,4-isopropylidenedioxyprolines (-)-4 and (+)4, respectively. Applying the Boc and Fmoc strategies of peptide synthesis, these compounds were used to construct two tripeptides containing the D- or L-2,3-trans-3,4-cis-4,5-trans-3,4-dihydroxy-5-hydroxymethylproline.

  DOI：

  10.1021/jo049637h

文献信息

• A Temperature‐Guided Diastereoselectivity Switch During the Desymmetrization of <i>meso</i> ‐7‐Azabicyclo[2.2.1]heptadiene: New Strategy towards the Synthesis of Aminocyclitols
  作者：Ganesh Pandey、Salla Rajender

  DOI：10.1002/chem.201100418

  日期：2011.5.27

  Strike while the iron is hot: A temperature‐guided diastereoselectivity switch has been observed in the desymmetrization of meso‐7‐azabicyclic alkadiene. Both enantiomeric forms of this bicyclic structural framework are formed by using either of the enantiomers of hydrobenzoin (see scheme; Boc=tert‐butyloxycarbonyl).

  打铁是热：一个温度引导非对映选择性开关已经在的desymmetrization已观察到内消旋-7-氮杂双环链二烯。该双环结构框架的两种对映体形式都是通过使用氢安息香的两种对映体形成的（见方案； Boc =叔丁氧羰基）。
• Synthesis of <scp>d</scp>- and <scp>l</scp>-2,3-<i>trans</i>-3,4-<i>cis</i>-4,5-<i>trans</i>-3,4-Dihydroxy-5-hydroxymethylproline and Tripeptides Containing Them
  作者：Antonio J. Moreno-Vargas、Inmaculada Robina、Elena Petricci、Pierre Vogel

  DOI：10.1021/jo049637h

  日期：2004.6.1

  Enantiomerically pure (-)-(1R,4R,5R,6S)- and (+)-(1S,4S,5S,6R)-7-(tert-butoxycarbonyl)-5,6-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]hept-2-one ((-)-3 and (+)-3) have been obtained from the Diels-Alder adduct of N-(tert-butoxycarbonyl)pyrrole and 2-bromo-1-(p-toluenesulfonyl)acetylene, including the Alexakis optical resolution of ketone ()-3 via formation of cyclic aminals with (1R,2R)diphenylethylenediamine. Compounds (-)-3 and (+)-3 were converted into D- and L-2,3-trans-3,4-cis-4,5-trans-N-(tert-butoxycarbonyl)-5-hydroxymethyl-3,4-isopropylidenedioxyprolines (-)-4 and (+)4, respectively. Applying the Boc and Fmoc strategies of peptide synthesis, these compounds were used to construct two tripeptides containing the D- or L-2,3-trans-3,4-cis-4,5-trans-3,4-dihydroxy-5-hydroxymethylproline.