α-(N⁴-Benzoyl)-5'-O-(tert-butyldimethylsilyl)-2'-deoxycytidine | 164070-15-9

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: α-(N⁴-Benzoyl)-5'-O-(tert-butyldimethylsilyl)-2'-deoxycytidine
• 英文别名: N-[1-[(2S,4S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-hydroxyoxolan-2-yl]-2-oxopyrimidin-4-yl]benzamide
• CAS: 164070-15-9
• 化学式: C₂₂H₃₁N₃O₅Si
• 分子量: 445.591
• InChiKey: CCPOWNJNXQQIFV-SCTDSRPQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.17
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  101
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  α-(N⁴-Benzoyl)-5'-O-(tert-butyldimethylsilyl)-2'-deoxycytidine 在 吡啶 、 二异丙基铵盐四氮唑 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 17.0h， 生成 α-<(N⁴-Benzoyl)-5'-O-<(N,N-diisopropylamino)(2-cyanoethoxy)phosphinyl>-3'-O-(di-p-methoxytrityl)-2'-deoxycytidine
  参考文献：
  名称：

  Synthesis and Physicochemical Properties of Alternating .alpha.,.beta.-Oligodeoxyribonucleotides with Alternating (3'.fwdarw.3')- and (5'.fwdarw.5')-Internucleotidic Phosphodiester Linkages

  摘要：

  A simple and straightforward synthesis of alpha-2'-deoxycytidine and alpha-2'-deoxyadenosine derivatives 6a,b has been achieved from commercial N-4-benzoyl-beta-2'-deoxycytidine and N-6-benzoyl-beta-2'-deoxyadenosine, respectively. Properly protected alpha-2'-deoxyribonucleosides 8a-d were converted to the corresponding 5'-phosphoramidite derivatives 9a-d. These and commercial beta-2'-deoxyribonucleoside 3'-phosphoramidites were readily incorporated into alternating alpha,beta-oligodeoxyribonucleotides with alternating (3'-->3')- and (5'-->5')-internucleotidic phosphodiester linkages by standard solid-phase synthesis methods. The alpha,beta-oligodeoxyribonucleotide 12 (Scheme 3) was considerably more resistant to hydrolysis catalyzed by snake venom phosphodiesterase, calf spleen phosphodiesterase, and S1 nuclease than the parent unmodified oligonucleotide 17 (Table 2). Thermal stability of the complex composed of 12 and complementary unmodified beta-oligomer 18 was comparable to that measured for the hybrid composed of the beta-oligodeoxyribonucleoside phosphorothioate 20 and 18 but less than that of the native DNA duplex 17:18 (Table 3). The differences in thermal stability (Delta T-m) and free energy of dissociation (Delta Delta G(37)degrees) observed between the duplex 12:18 and the singly mismatched complex 12:19 (9 degrees C and -2.5 kcal/mol, respectively) (Tables 3 and 4) suggest that the sequence specificity;of 12 toward a complementary unmodified beta-DNA oligomer is comparable to that of 17. In addition, the CD spectrum of 12:18 at 22 degrees C resembles more closely that of the natural DNA duplex 17:18 than that of the alpha,beta-DNA duplex 12:13 (Figure 3). These findings indicate that the duplex 12:18 exhibits, at least to some extent, a B-type helicity. The alpha,beta-oligodeoxyribonucleotide 12 formed also a complex with the complementary beta-oligoribonucleotide 23 but with much reduced affinity (T-m = 35 degrees C) than that measured with the complementary DNA sequence 18 (T-m = 54 degrees C). CD spectroscopy indicated that the complex 12:23 adopted a conformation similar to that observed for duplex 17:23 at 22 degrees C. Unlike the DNA-RNA heteroduplex 17:23, the complex 12:23 was not a substrate for E. coli RNase H.

  DOI：

  10.1021/jo00111a009
• 作为产物：
  描述：

  N-苯甲酰-2'-脱氧胞苷 在 咪唑 、 N,O-双三甲硅基乙酰胺 、 碳酸氢钠 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 25.0h， 生成 α-(N⁴-Benzoyl)-5'-O-(tert-butyldimethylsilyl)-2'-deoxycytidine
  参考文献：
  名称：

  Synthesis and Physicochemical Properties of Alternating .alpha.,.beta.-Oligodeoxyribonucleotides with Alternating (3'.fwdarw.3')- and (5'.fwdarw.5')-Internucleotidic Phosphodiester Linkages

  摘要：

  A simple and straightforward synthesis of alpha-2'-deoxycytidine and alpha-2'-deoxyadenosine derivatives 6a,b has been achieved from commercial N-4-benzoyl-beta-2'-deoxycytidine and N-6-benzoyl-beta-2'-deoxyadenosine, respectively. Properly protected alpha-2'-deoxyribonucleosides 8a-d were converted to the corresponding 5'-phosphoramidite derivatives 9a-d. These and commercial beta-2'-deoxyribonucleoside 3'-phosphoramidites were readily incorporated into alternating alpha,beta-oligodeoxyribonucleotides with alternating (3'-->3')- and (5'-->5')-internucleotidic phosphodiester linkages by standard solid-phase synthesis methods. The alpha,beta-oligodeoxyribonucleotide 12 (Scheme 3) was considerably more resistant to hydrolysis catalyzed by snake venom phosphodiesterase, calf spleen phosphodiesterase, and S1 nuclease than the parent unmodified oligonucleotide 17 (Table 2). Thermal stability of the complex composed of 12 and complementary unmodified beta-oligomer 18 was comparable to that measured for the hybrid composed of the beta-oligodeoxyribonucleoside phosphorothioate 20 and 18 but less than that of the native DNA duplex 17:18 (Table 3). The differences in thermal stability (Delta T-m) and free energy of dissociation (Delta Delta G(37)degrees) observed between the duplex 12:18 and the singly mismatched complex 12:19 (9 degrees C and -2.5 kcal/mol, respectively) (Tables 3 and 4) suggest that the sequence specificity;of 12 toward a complementary unmodified beta-DNA oligomer is comparable to that of 17. In addition, the CD spectrum of 12:18 at 22 degrees C resembles more closely that of the natural DNA duplex 17:18 than that of the alpha,beta-DNA duplex 12:13 (Figure 3). These findings indicate that the duplex 12:18 exhibits, at least to some extent, a B-type helicity. The alpha,beta-oligodeoxyribonucleotide 12 formed also a complex with the complementary beta-oligoribonucleotide 23 but with much reduced affinity (T-m = 35 degrees C) than that measured with the complementary DNA sequence 18 (T-m = 54 degrees C). CD spectroscopy indicated that the complex 12:23 adopted a conformation similar to that observed for duplex 17:23 at 22 degrees C. Unlike the DNA-RNA heteroduplex 17:23, the complex 12:23 was not a substrate for E. coli RNase H.

  DOI：

  10.1021/jo00111a009

文献信息

• Synthesis and Physicochemical Properties of Alternating .alpha.,.beta.-Oligodeoxyribonucleotides with Alternating (3'.fwdarw.3')- and (5'.fwdarw.5')-Internucleotidic Phosphodiester Linkages
  作者：Masakazu Koga、Andrzej Wilk、Michael F. Moore、Carlo L. Scremin、Liang Zhou、Serge L. Beaucage

  DOI：10.1021/jo00111a009

  日期：1995.3

  A simple and straightforward synthesis of alpha-2'-deoxycytidine and alpha-2'-deoxyadenosine derivatives 6a,b has been achieved from commercial N-4-benzoyl-beta-2'-deoxycytidine and N-6-benzoyl-beta-2'-deoxyadenosine, respectively. Properly protected alpha-2'-deoxyribonucleosides 8a-d were converted to the corresponding 5'-phosphoramidite derivatives 9a-d. These and commercial beta-2'-deoxyribonucleoside 3'-phosphoramidites were readily incorporated into alternating alpha,beta-oligodeoxyribonucleotides with alternating (3'-->3')- and (5'-->5')-internucleotidic phosphodiester linkages by standard solid-phase synthesis methods. The alpha,beta-oligodeoxyribonucleotide 12 (Scheme 3) was considerably more resistant to hydrolysis catalyzed by snake venom phosphodiesterase, calf spleen phosphodiesterase, and S1 nuclease than the parent unmodified oligonucleotide 17 (Table 2). Thermal stability of the complex composed of 12 and complementary unmodified beta-oligomer 18 was comparable to that measured for the hybrid composed of the beta-oligodeoxyribonucleoside phosphorothioate 20 and 18 but less than that of the native DNA duplex 17:18 (Table 3). The differences in thermal stability (Delta T-m) and free energy of dissociation (Delta Delta G(37)degrees) observed between the duplex 12:18 and the singly mismatched complex 12:19 (9 degrees C and -2.5 kcal/mol, respectively) (Tables 3 and 4) suggest that the sequence specificity;of 12 toward a complementary unmodified beta-DNA oligomer is comparable to that of 17. In addition, the CD spectrum of 12:18 at 22 degrees C resembles more closely that of the natural DNA duplex 17:18 than that of the alpha,beta-DNA duplex 12:13 (Figure 3). These findings indicate that the duplex 12:18 exhibits, at least to some extent, a B-type helicity. The alpha,beta-oligodeoxyribonucleotide 12 formed also a complex with the complementary beta-oligoribonucleotide 23 but with much reduced affinity (T-m = 35 degrees C) than that measured with the complementary DNA sequence 18 (T-m = 54 degrees C). CD spectroscopy indicated that the complex 12:23 adopted a conformation similar to that observed for duplex 17:23 at 22 degrees C. Unlike the DNA-RNA heteroduplex 17:23, the complex 12:23 was not a substrate for E. coli RNase H.