(+/-)-2-azabicyclo<2.2.2>oct-5-en-3-one | 39170-54-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (+/-)-2-azabicyclo<2.2.2>oct-5-en-3-one
• 英文别名: 2-azabicyclo<2.2.2>oct-5-en-3-one；2-azabicyclo[2.2.2]oct-5-en-3-one；2-aza-bicyclo[2.2.2]oct-5-en-3-one；2-Azabicyclo<2.2.2>oct-5-en-3-on；5-Azabicyclo<2.2.2>oct-2-en-6-on
• CAS: 39170-54-2
• 化学式: C₇H₉NO
• mdl: MFCD19217484
• 分子量: 123.155
• InChiKey: ZIGCILRNWVQSNC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.571
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-2-azabicyclo<2.2.2>oct-5-en-3-one 在 盐酸 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 phosphate buffer pH 7.0 、 氨 、 sodium acetate 、 溶剂黄146 、 三乙胺 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 、 锌 、 sodium nitrite 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 100.0h， 生成 (R)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid (1S,4R)-4-(2-amino-6-oxo-1,6-dihydro-purin-9-yl)-cyclohex-2-enylmethyl ester
  参考文献：
  名称：

  Deamination of 9-(Hydroxymethylated cycloalkyl)-9H-adenines (Carbocyclic Adenine Nucleosides) by Adenosine Deaminase: Effect of High-Pressure Upon Deamination Rate and Enantioselectivity

  摘要：

  The deamination of eight kinds of racemic carbocyclic adenine nucleosides by adenosine deaminase under high-pressure (400 MPa) was examined and the result was compared with that obtained from the reaction under atmospheric pressure. The deamination of all carbocyclic nucleosides irrespective to their ring size of carbocycles was facilitated remarkably by high-pressure. The reaction of three and five membered carbocyclic pressure whereas the enantioselectivity of six membered carbocyclic nucleosides was suppressed under high-pressure. However, the enantioselectivity of four membered nucleosides was low under both conditions.

  DOI：

  10.1080/07328319608002411
• 作为产物：
  描述：

  苯磺酰氰化物 、 1,3-环己二烯 反应 48.0h， 以43%的产率得到(+/-)-2-azabicyclo<2.2.2>oct-5-en-3-one
  参考文献：
  名称：

  Deamination of 9-(Hydroxymethylated cycloalkyl)-9H-adenines (Carbocyclic Adenine Nucleosides) by Adenosine Deaminase: Effect of High-Pressure Upon Deamination Rate and Enantioselectivity

  摘要：

  The deamination of eight kinds of racemic carbocyclic adenine nucleosides by adenosine deaminase under high-pressure (400 MPa) was examined and the result was compared with that obtained from the reaction under atmospheric pressure. The deamination of all carbocyclic nucleosides irrespective to their ring size of carbocycles was facilitated remarkably by high-pressure. The reaction of three and five membered carbocyclic pressure whereas the enantioselectivity of six membered carbocyclic nucleosides was suppressed under high-pressure. However, the enantioselectivity of four membered nucleosides was low under both conditions.

  DOI：

  10.1080/07328319608002411

文献信息

• Process for the preparation of aminoalcohol derivatives and their further conversion to (1R, 4S)-4-((2-amino-6-chloro-5-formamido-4-pyrimidinyl)-amino)-2-cyclopentenyl-1- methanol
  申请人：Lonza AG

  公开号：US20020010360A1

  公开（公告）日：2002-01-24

  The invention relates to a novel process for the preparation of an aminoalcohol of the formula 1 racemically or optically active, starting from 2-azabi-cyclo[2.2.1]hept-5-en-3-one, its further conversion to give the corresponding acyl derivative and its further conversion to (1S,4R)- or (1R,4S)-4-(2-amino-6-chloro-9-H-purine-9-yl)-2-cyclopentenyl-1-methanol of the formulae 2 In the latter synthesis, the aminoalcohol is converted into the corresponding D- or L-tartrate, which is then reacted with N-(2-amino-4,6-dichloropyrimidin-5-yl) formamide of the formula 3 to give (1S,4R)- or (1R,4S)-4-[(2-amino-6-chloro-5-formamido-4-pyrimidinyl)amino]-2-cyclopentenyl-1-methanol of the formulae 4 and then cyclized to give the end compounds.

  该发明涉及一种新颖的方法，用于制备公式1的氨基醇，其为外消旋或光学活性，从2-azabi-cyclo［2.2.1］hept-5-en-3-one出发，进一步转化为相应的酰基衍生物，再进一步转化为公式2中的(1S,4R)-或(1R,4S)-4-(2-氨基-6-氯-9-H-嘌呤-9-基)-2-环戊烯基-1-甲醇。在后一合成中，氨基醇转化为相应的D-或L-酒石酸盐，然后与公式3中的N-(2-氨基-4,6-二氯嘧啶-5-基)甲酰胺反应，以得到公式4中的(1S,4R)-或(1R,4S)-4-(2-氨基-6-氯-5-甲酰胺基-4-嘧啶基)氨基-2-环戊烯基-1-甲醇，然后进行环化反应以得到最终的化合物。
• Synthesis of Pyrrolizidine, Indolizidine, and Quinolizidine Derivatives Using Ruthenium-Catalyzed Ring-Opening Metathesis and Ring-Closing Metathesis of Cycloalkene-ynes
  作者：Hideaki Wakamatsu、Yoshihiro Sato、Reiko Fujita、Miwako Mori

  DOI：10.1002/adsc.200600539

  日期：2007.5.7

  in good yield, which could be converted to a pyrrolizidine derivative. Furthermore, ROM-RCM of azabicyclo[2.2.1]heptene-ynes using the second-generation Grubbs’ catalyst was investigated. When an azabicycloheptene derivative was exposed to a catalytic amount of a ruthenium carbene complex, pyrrolizidine and indolizidine derivatives were obtained in good yields. The distribution of these products depends

  使用第一代和第二代Grubbs催化剂证明了具有酯部分的环戊烯炔的开环易位和闭环易位（ROM-RCM）。当在室温下在乙烯气氛下在5摩尔％钌卡宾配合物的存在下进行环烯炔的反应时，ROM-RCM顺利进行，以高收率得到吡咯烷衍生物，可以将其转化为环戊烯衍生物。吡咯嗪核苷衍生物。此外，研究了使用第二代格鲁布斯催化剂的氮杂双环[2.2.1]庚烯-炔的ROM-RCM。当将氮杂双环庚烯衍生物暴露于催化量的钌卡宾配合物时，以良好的收率获得了吡咯烷定和吲哚并立定衍生物。这些产物的分布取决于炔烃上的取代基。当氮杂双环[2。如图1b所示，获得了作为主要产物的吡咯嗪核苷衍生物。尽管产率适中，但具有1b的氮杂双环[2.2.2]辛烯-炔的ROM-RCM提供了喹oli嗪衍生物20。
• Stereospecific Synthesis of cis-2,4-Pyrrolidinedicarboxylic Acid and cis-2,5-Piperidinedicarboxylic Acid.
  作者：Yasushi ARAKAWA、Mika YASUDA、Masafumi OHNISHI、Shigeyuki YOSHIFUJI

  DOI：10.1248/cpb.45.255

  日期：——

  Lactams derived from hetero Diels-Alder adducts were stereospecifically converted into cis-2, 4-pyrrolidinedicarboxylic acid and cis-2, 5-piperidinedicarboxylic acid by ruthenium tetroxide oxidation. Optically active (2S, 4S)-(-)-2, 4-pyrrolidinedicarboxylic acid and (2R, 4R)-(+)-2, 4-pyrrolidinedicarboxylic acid were synthesized from (1S, 4R)-(+)-2-azabicyclo[2.2.1]hept-5-en-3-one and (1R, 4S)-(-)-2-azabicyclo[2.2.1]hept-5-en-3-one, respectively.

  来自杂环Diels-Alder加合物的内酰胺通过钌四氧化物氧化被立体特异性地转化为顺-2, 4-吡咯烷二羧酸和顺-2, 5-哌啶二羧酸。光学活性的（2S, 4S）-(-)-2, 4-吡咯烷二羧酸和（2R, 4R）-(+)-2, 4-吡咯烷二羧酸分别是从（1S, 4R）-(+)-2-氮杂双环[2.2.1]庚-5-烯-3-酮和（1R, 4S）-(-)-2-氮杂双环[2.2.1]庚-5-烯-3-酮合成的。
• Process for the preparation of aminoalcohol derivatives and their further conversion to (1R,4S)-4-(2-amino-6-chloro-5-formamido-4-pyrimidinyl)-amino)-2-cyclopentenyl-1-methanol
  申请人：——

  公开号：US20040142436A1

  公开（公告）日：2004-07-22

  The invention relates to a novel process for the preparation of an aminoalcohol of the formula 1 racemically or optically active, starting from 2-azabicyclo[2.2.1]hept-5-en-3-one, its further conversion to give the corresponding acyl derivative and its further conversion to (1S,4R)- or (1R,4S)-4-(2-amino-6-chloro-9-H-purine-9-yl)-2-cyclopentenyl-1-methanol of the formulae 2 In the latter synthesis, the aminoalcohol is converted into the corresponding D- or L-tartrate, which is then reacted with N-(2-amino-4,6-dichloropyrimidin-5-yl) form amide of the formula 3 to give (1S,4R)- or (1R,4S)-4-[(2-amino-6-chloro-5-formamido-4-pyrimidinyl)amino]-2-cyclopentenyl-1-methanol of the formulae 4 and then cyclized to give the end compounds.

  本发明涉及一种从2-氮杂双环[2.2.1]庚-5-烯-3-酮出发制备公式1的氨基醇的新工艺，其进一步转化为相应的酰基衍生物，并进一步转化为公式2的(1S,4R)-或(1R,4S)-4-(2-氨基-6-氯-9-H-嘌呤-9-基)-2-环戊基-1-甲醇。在后一种合成中，氨基醇转化为相应的D-或L-酒石酸盐，然后与公式3的N-(2-氨基-4,6-二氯嘧啶-5-基)甲酰胺反应，以给出公式4的(1S,4R)-或(1R,4S)-4-[(2-氨基-6-氯-5-甲酰基-4-嘧啶基)氨基]-2-环戊基-1-甲醇，然后环化以得到最终产物。
• PROCESS FOR THE PREPARATION OF AMINOALCOHOL DERIVATIVES AND THEIR FURTHER CONVERSION TO (1R, 4S)-4(2-AMINO-6-CHLORO-5-FORMAMIDO-4- PYRIMIDINYL)-AMINO-2-CYCLOPENTENYL-1-METHANOL
  申请人：Brieden Walter

  公开号：US20060211862A1

  公开（公告）日：2006-09-21

  The invention relates to a novel process for the preparation of an aminoalcohol of the formula racemically or optically active, starting from 2-azabicyclo[2.2.1]hept-5-en-3-one, its further conversion to give the corresponding acyl derivative and its further conversion to (1S,4R)- or ( 1 R,4S)-4-(2-amino-6-chloro-9-H-purine-9-yl)-2-cyclopentenyl-1-methanol of the formulae In the latter synthesis, the aminoalcohol is converted into the corresponding D- or L-tartrate, which is then reacted with N-(2-amino-4,6-dichloropyrimidin-5-yl) formamide of the formula to give (1S,4R)- or (1R,4S)-4-[(2-amino-6-chloro-5-formamido-4-pyrimidinyl)amino]-2-cyclopentenyl-1-methanol of the formulae and then cyclized to give the end compounds.

  本发明涉及一种新型的制备氨基醇的方法，该氨基醇的结构式为，可以是外消旋或内消旋，从2-氮杂双环[2.2.1]庚-5-烯-3-酮开始，进一步转化为相应的酰基衍生物，然后进一步转化为(1S,4R)-或(1R,4S)-4-(2-氨基-6-氯-9-H-嘌呤-9-基)-2-环戊烯基-1-甲醇，其结构式为。在后一种合成中，氨基醇转化为相应的D-或L-酒石酸盐，然后与N-(2-氨基-4,6-二氯嘧啶-5-基)甲酰胺反应，其结构式为，以给出(1S,4R)-或(1R,4S)-4-[(2-氨基-6-氯-5-甲酰基-4-嘧啶基)氨基]-2-环戊烯基-1-甲醇，其结构式为，然后环化以得到最终化合物。