(+/-)-5-methyl-1-<4-(hydroxymethyl)-3-cyclopentenyl>-2,4(1H,3H)-pyrimidinedione | 161168-72-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: (+/-)-5-methyl-1-<4-(hydroxymethyl)-3-cyclopentenyl>-2,4(1H,3H)-pyrimidinedione
• 英文别名: (+/-)-1-[3-(Hydroxymethyl)cyclopent-3-en-1-yl]-5-methylpyrimidine-2(1H),4(3H)-dione；(+/-)-1-[4-(hydroxymethyl)cyclopent-3-en-1-yl]thymine；1-[3-(Hydroxymethyl)cyclopent-3-en-1-yl]-5-methylpyrimidine-2,4-dione
• CAS: 161168-72-5
• 化学式: C₁₁H₁₄N₂O₃
• 分子量: 222.244
• InChiKey: UVVCEOFVULZRIK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  69.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-5-methyl-1-<4-(hydroxymethyl)-3-cyclopentenyl>-2,4(1H,3H)-pyrimidinedione 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以31%的产率得到(+/-)-trans-1-[3,4-epoxy-3-(hydroxymethyl)cyclopentyl]thymine
  参考文献：
  名称：

  New and Efficient Synthesis of Racemic Cyclopent-3-en-1-yl Nucleoside Analogues and Their Derivatives

  摘要：

  已开发出一种新的高效合成方法，从环戊二烯出发合成了外消旋环戊-3-烯-1-基核苷类似物。关键步骤是对中间形成的两种烷基化环戊二烯混合物进行区域选择性氢硼化，得到一个环戊醇。剩余的双键进一步通过氢硼化、环氧化、顺式羟基化和环丙烷化进行官能化。

  DOI：

  10.1135/cccc20061011
• 作为产物：
  描述：

  (+/-)-3-[(benzyloxy)methyl]cyclopent-3-en-1-ol 在 sodium hydroxide 、 偶氮二甲酸二异丙酯 、 三氯化硼 、 三苯基膦 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 生成 (+/-)-5-methyl-1-<4-(hydroxymethyl)-3-cyclopentenyl>-2,4(1H,3H)-pyrimidinedione
  参考文献：
  名称：

  New and Efficient Synthesis of Racemic Cyclopent-3-en-1-yl Nucleoside Analogues and Their Derivatives

  摘要：

  已开发出一种新的高效合成方法，从环戊二烯出发合成了外消旋环戊-3-烯-1-基核苷类似物。关键步骤是对中间形成的两种烷基化环戊二烯混合物进行区域选择性氢硼化，得到一个环戊醇。剩余的双键进一步通过氢硼化、环氧化、顺式羟基化和环丙烷化进行官能化。

  DOI：

  10.1135/cccc20061011

文献信息

• A New and Short Convergent Synthetic Strategy to Carbocyclic Nucleosides
  作者：Bastian Reichardt、Chris Meier

  DOI：10.1080/15257770701507937

  日期：2007.11.26

  An efficient synthesis for racemic cyclopent-3-en-1-yl nucleoside analogues has been developed starting from cyclopentadiene. The key step is the regioselective hydroboration of a mixture of intermediate alkylatede cyclopentadienes to give one cyclopentenol.

  外消旋环戊-3-烯-1-基核苷类似物的有效合成已从环戊二烯开始。关键步骤是中间体烷基化环戊二烯混合物的区域选择性硼氢化反应得到一种环戊烯醇。
• Synthesis of Carbocyclic 4'-C-Hydroxymethyl Analogues of Azidodeoxythymidine, Deoxythymidine, Deoxydidehydrothymidine and Thymidine Carba Analogue with Fused Oxetane Ring
  作者：Hubert Hřebabecký、Antonín Holý

  DOI：10.1135/cccc20000395

  日期：——

  Tosylation of (±)-1-[trans-4-hydroxy-3,3-bis(hydroxymethyl)cyclopentyl]-5-methylpyrimidine-2(1H),4(3H)-dione (1) and (±)-1-[cis-4-hydroxy-3,3-bis(hydroxymethyl)cyclopentyl]-5-methylpyrimidine-2(1H),4(3H)-dione (2) and treatment of the obtained 1-(1R*,3R*,4S*)- 4-hydroxy-3-(hydroxymethyl)-3-[(tosyloxy)methyl]cyclopentyl}-5-methylpyrimidine- 2(1H),4(3H)-dione (6) and 1-(1R*,3S*,4R*)-4-hydroxy-3-(hydroxymethyl)-3-[(tosyloxy)- methyl]cyclopentyl}-5-methylpyrimidine-2(1H),4(3H)-dione (9) with methanolic sodium methoxide gave 1-[(1R*,4S*,6S*)-4-hydroxymethyl-2-oxabicyclo[3.2.0]hept-6-yl]-5-methylpyrimidine-2(1H),4(3H)-dione (7) and 1-[(1R*,4S*,6R*)-4-hydroxymethyl-2-oxabicyclo[3.2.0]hept-6-yl]-5-methylpyrimidine-2(1H),4(3H)-dione (10), respectively. Treatment of (±)-1-cis-4-mesyloxy-3,3-bis[(trityloxy)methyl]cyclopentyl}-5-methylpyrimidine-2(1H),4(3H)-dione (11), which was prepared from 2 by tritylation and mesylation, with 1,8-diazabicyclo[5.4.0]undec-7-ene in dimethylformamide afforded after deprotection (±)-1-[4,4-bis(hydroxymethyl)cyclopent-2-en-1-yl]-5-methylpyrimidine-2(1H),4(3H)-dione (14). Hydrogen- ation of 14 led to (±)-1-[3,3-bis(hydroxymethyl)cyclopentyl]-5-methylpyrimidine-2(1H),4(3H)- dione (15). (±)-1-trans-4-Mesyloxy-3,3-bis[(trityloxy)methyl]cyclopentyl}-5-methylpyrimidine- 2(1H),4(3H)-dione (17), which was prepared from 1, was converted to (1R*,9R*)-6-methyl-5-oxo-11,11-bis(trityloxymethyl)-2-oxa-4,8-diazatricyclo[7.2.1.0^3,8]dodec-3,6-diene (18). The compound 18 was deprotected and heated with lithium azide in dimethylformamide to give (±)-1-[trans-4-azido-3,3-bis(hydroxymethyl)cyclopentyl]-5-methylpyrimidine-2(1H),4(3H)-dione (21).

  对(±)-1-[trans-4-羟基-3,3-双(羟甲基)环戊基]-5-甲基嘧啶-2(1H),4(3H)-二酮 (1)和(±)-1-[cis-4-羟基-3,3-双(羟甲基)环戊基]-5-甲基嘧啶-2(1H),4(3H)-二酮 (2)进行甲苯磺酸化反应，得到1-(1R*,3R*,4S*)-4-羟基-3-(羟甲基)-3-[(对甲苯磺酰氧)甲基]环戊基}-5-甲基嘧啶-2(1H),4(3H)-二酮 (6)和1-(1R*,3S*,4R*)-4-羟基-3-(羟甲基)-3-[(对甲苯磺酰氧)甲基]环戊基}-5-甲基嘧啶-2(1H),4(3H)-二酮 (9)。将得到的化合物与甲醇钠甲醇溶液反应，得到1-[(1R*,4S*,6S*)-4-羟甲基-2-氧杂双环[3.2.0]庚-6-基]-5-甲基嘧啶-2(1H),4(3H)-二酮 (7)和1-[(1R*,4S*,6R*)-4-羟甲基-2-氧杂双环[3.2.0]庚-6-基]-5-甲基嘧啶-2(1H),4(3H)-二酮 (10)。将(±)-1-cis-4-甲磺氧基-3,3-双[(三苯甲氧基)甲基]环戊基}-5-甲基嘧啶-2(1H),4(3H)-二酮 (11)与1,8-二氮杂双环[5.4.0]十一碳-7-烯在二甲基甲酰胺中反应，去保护后得到(±)-1-[4,4-双(羟甲基)环戊-2-烯基]-5-甲基嘧啶-2(1H),4(3H)-二酮 (14)。对14进行氢化反应，得到(±)-1-[3,3-双(羟甲基)环戊基]-5-甲基嘧啶-2(1H),4(3H)-二酮 (15)。从1制备(±)-1-trans-4-甲磺氧基-3,3-双[(三苯甲氧基)甲基]环戊基}-5-甲基嘧啶-2(1H),4(3H)-二酮 (17)，并将其转化为(1R*,9R*)-6-甲基-5-氧代-11,11-双(三苯甲氧基甲基)-2-氧杂四环[7.2.1.0^3,8]十二碳-3,6-二烯 (18)。将化合物18去保护并在二甲基甲酰胺中与锂叠氮化合物加热反应，得到(±)-1-[trans-4-叠氮基-3,3-双(羟甲基)环戊基]-5-甲基嘧啶-2(1H),4(3H)-二酮 (21)。
• Carbocyclic Analogues of 3′,4′-Didehydro-2′-deoxyribofuranosyl-2,4(1<i>H</i>,3<i>H</i>)-pyrimidinediones
  作者：C. Allen O'Dell、Y. Fulmer Shealy

  DOI：10.1080/15257779408010673

  日期：1994.9

  A new method for obtaining carbocyclic analogues of 3',4'-didehydro-2,4(1H,3H)-pyrimidinedione nucleosides in good yields consists of the reaction of the carbocyclic 2,3'-anhydronucleosides with lithium chloride in dimethylformamide. Small amounts of the carbocyclic 2',3'-didehydro isomers are formed simultaneously. The carbocyclic 2,3'-anhydronucleosides were obtained by treating carbocyclic 5'-trityl derivatives with DAST.
• New and Efficient Synthesis of Racemic Cyclopent-3-en-1-yl Nucleoside Analogues and Their Derivatives
  作者：Bastian Reichardt、Olaf R. Ludek、Chris Meier

  DOI：10.1135/cccc20061011

  日期：——

  A new, efficient synthesis of racemic cyclopent-3-en-1-yl nucleoside analogues has been developed starting from cyclopentadiene. The key step is the regioselective hydroboration of an intermediately formed mixture of two alkylated cyclopentadienes to give one cyclopentenol. The remaining double bond was further functionalized by hydroboration, epoxidation, cis-hydroxylation and cyclopropanation.

  已开发出一种新的高效合成方法，从环戊二烯出发合成了外消旋环戊-3-烯-1-基核苷类似物。关键步骤是对中间形成的两种烷基化环戊二烯混合物进行区域选择性氢硼化，得到一个环戊醇。剩余的双键进一步通过氢硼化、环氧化、顺式羟基化和环丙烷化进行官能化。