3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2'-deoxy-2'-methyleneadenosine | 104409-40-7

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷
• 英文名称: 3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2'-deoxy-2'-methyleneadenosine
• 英文别名: 9-(2-deoxy-3,5-O-(tetraisopropyldisiloxanediyl)-2-methylene-β-D-erythro-pentofuranosyl)adenine；3',5'-O-(tetraisopropyldisiloxane-1,3-diyl)-2'-deoxy-2'-methylideneadenosine；9-[(6aR,8R,9aS)-9-methylidene-2,2,4,4-tetra(propan-2-yl)-6a,9a-dihydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]purin-6-amine
• CAS: 104409-40-7
• 化学式: C₂₃H₃₉N₅O₄Si₂
• 分子量: 505.765
• InChiKey: BHFDESBVAGKEGI-QMHWCDLVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  34
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  107
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2'-deoxy-2'-methyleneadenosine 在 咪唑 、 4-二甲氨基吡啶 、 二苯甲酮 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 54.0h， 生成 5'-O-TBDMS-2'-deoxy-3'-O-(phenoxythiocarbonyl)adenosine-2'-spirocyclopropane
  参考文献：
  名称：

  Nucleic acid and related compounds. 75. Synthesis and radical-induced ring-opening reactions of 2'-deoxyadenosine-2'-spirocyclopropane and its uridine analogs. Mechanistic probes for ribonucleotide reductases

  摘要：

  DOI：

  10.1021/ja00036a077
• 作为产物：
  描述：

  3,5-O-(1,1,3,3-四异丙基-1,3-二硅氧烷)腺苷 在 吡啶 、 chromium(VI) oxide 、 乙酸酐 、 sodium tert-pentoxide 作用下， 以 二氯甲烷 为溶剂， 反应 51.0h， 生成 3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2'-deoxy-2'-methyleneadenosine
  参考文献：
  名称：

  Nucleic acid related compounds. 70. Synthesis of 2'(and 3')-deoxy-2'(and 3')-methyleneadenosines and bis(methylene)furan 4',5'-didehydro-5'-deoxy-2'(and 3')-methyleneadenosines. Inhibitors of S-adenosyl-L-homocysteine hydrolase and ribonucleotide reductase

  摘要：

  Wittig treatment of 3',5'(or 2',5')-bis-O-silyl-2'(or 3')-ketoadenosine derivatives with methylenetriphenylphosphorane and deprotection gave the 2'(or 3')-deoxy-2'(or 3')-methyleneadenosines, respectively. Enzymatic deamination afforded the 2'(or 3')-deoxy-2'(or 3')-methyleneinosines. Treatment of 2'-O-(tert-butyldimethylsilyl)-3'-deoxy-3'-methylene-5'-O-tosyladenosine (14) with sodium 2-methyl-2-butoxide and deprotection gave 9-(3,5-dideoxy-3-methylene-beta-D-glycero-pent-4-enofuranosyl)adenine (20). Analogous treatment of a protected 2',5'-dideoxy-5'-iodo-2'-methyleneadenosine derivative gave 9-(2,5-dideoxy-2-methylene-beta-D-glycero-pent-4-enofuranosyl)adenine (22). Biochemical aspects of the putative mechanism-based inhibition of S-adenosyl-L-homocysteine hydrolase and ribonucleotide reductase by these compounds are discussed.

  DOI：

  10.1021/jo00025a029

文献信息

• Nucleosides and nucleotides. LXV Synthesis of 8,2'-methano- and 8,2'-ethanoadenosines.
  作者：HIROYUKI USUI、TOHRU UEDA

  DOI：10.1248/cpb.34.1518

  日期：——

  Treatment of 3', 5'-O-(tetraisopropyldisiloxane-1, 3-diyl)-2'-ketoadenosine (1) with methylenetriphenylphosphorane gave the 2'-methylene derivative (2). Hydroxylation of 1 with OsO4 gave the 2'-hydroxymethyladenosine (4), which was then converted to the 2'-phenylthiomethyl derivative (5). Photocyclization followed by deprotection of the product furnished 8, 2'-methanoadenosine (7), and adenosine fixed in a high-anti conformation. Oxidation of a 2'-hydroxyethylideneadenosine with OsO4 gave the 2'-dihydroxyethyladenosine (10), which was also converted to the 2'-(2-phenylthioethyl) derivative (11). The photocyclization of 11 and successive elimination of the hydroxyl group gave the 8, 2'-ethenoadenosine (13). Catalytic hydrogenation and deprotection of 13 afforded 8, 2'-ethanoadenosine (15). The circular dichroism spectral features of C-cycloadenosine are discussed.

  将 3'，5'-O-(四异丙基二硅氧烷-1，3-二基)-2'-酮腺苷 (1) 与亚甲基三苯基膦处理，可得到 2'-亚甲基衍生物 (2)。用 OsO4 对 1 进行羟基化反应，得到 2'- 羟甲基腺苷 (4)，然后将其转化为 2'- 苯硫甲基衍生物 (5)。对产物进行光环化和脱保护处理后，得到 8、2'-甲基腺苷（7）和以高反构象固定的腺苷。用 OsO4 氧化 2'-hydroxyethylideneadenosine 可以得到 2'-dihydroxyethyladenosine (10)，它还可以转化为 2'-(2-phenylthioethyl) 衍生物 (11)。11 的光环化和羟基的连续消除得到了 8,2'-乙烯腺苷（13）。对 13 进行催化氢化和脱保护处理后，得到了 8，2'-乙烯腺苷（15）。本文讨论了 C-胞二色谱的光谱特征。
• Nucleic acid related compounds. 70. Synthesis of 2'(and 3')-deoxy-2'(and 3')-methyleneadenosines and bis(methylene)furan 4',5'-didehydro-5'-deoxy-2'(and 3')-methyleneadenosines. Inhibitors of S-adenosyl-L-homocysteine hydrolase and ribonucleotide reductase
  作者：Vicente Samano、Morris J. Robins

  DOI：10.1021/jo00025a029

  日期：1991.12

  Wittig treatment of 3',5'(or 2',5')-bis-O-silyl-2'(or 3')-ketoadenosine derivatives with methylenetriphenylphosphorane and deprotection gave the 2'(or 3')-deoxy-2'(or 3')-methyleneadenosines, respectively. Enzymatic deamination afforded the 2'(or 3')-deoxy-2'(or 3')-methyleneinosines. Treatment of 2'-O-(tert-butyldimethylsilyl)-3'-deoxy-3'-methylene-5'-O-tosyladenosine (14) with sodium 2-methyl-2-butoxide and deprotection gave 9-(3,5-dideoxy-3-methylene-beta-D-glycero-pent-4-enofuranosyl)adenine (20). Analogous treatment of a protected 2',5'-dideoxy-5'-iodo-2'-methyleneadenosine derivative gave 9-(2,5-dideoxy-2-methylene-beta-D-glycero-pent-4-enofuranosyl)adenine (22). Biochemical aspects of the putative mechanism-based inhibition of S-adenosyl-L-homocysteine hydrolase and ribonucleotide reductase by these compounds are discussed.
• Nucleic acid and related compounds. 75. Synthesis and radical-induced ring-opening reactions of 2'-deoxyadenosine-2'-spirocyclopropane and its uridine analogs. Mechanistic probes for ribonucleotide reductases
  作者：Vicente Samano、Morris J. Robins

  DOI：10.1021/ja00036a077

  日期：1992.5