9-[5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-β-D-glycero-pent-2-enofuranosyl]adenine | 141684-87-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 咪唑并嘧啶类
• 英文名称: 9-[5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-β-D-glycero-pent-2-enofuranosyl]adenine
• 英文别名: 9-[(2R,5S)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-2,5-dihydrofuran-2-yl]purin-6-amine
• CAS: 141684-87-9
• 化学式: C₂₆H₂₉N₅O₂Si
• 分子量: 471.634
• InChiKey: BXIRIAFDCYTWSL-SIKLNZKXSA-N

物化性质

• 沸点：
  612.3±65.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.44
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  88.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  9-[5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-β-D-glycero-pent-2-enofuranosyl]adenine 在 氟化铵 作用下， 以 甲醇 为溶剂， 反应 5.0h， 以88%的产率得到2,3-二脱氧-2,3-二氢腺苷
  参考文献：
  名称：

  核酸相关化合物。105.由核糖核环2'，3'-（硫酸盐或磷酸盐）或2'，3'-二甲磺酸盐通过萘二甲酸钠（1）的还原消除反应合成2'，3'-Didehydro-2'，3'-二脱氧核苷。

  摘要：

  用亚硫酰氟处理嘌呤核糖核苷导致形成环状2'，3'-亚硫酸酯。5'-羟基的乙酰化和Sharpless氧化（NaIO（4）/ RuCl（3））得到环状2'，3'-硫酸酯衍生物。用亚硫酰氯处理5'-O-甲硅烷基保护的核糖核苷，然后氧化，得到了环状2'，3'-硫酸盐的另一种途径。用萘钠（THF / -50℃）还原消除，得到2′，3′-不饱和核苷。腺苷环2'，3'-磷酸的平行处理得到2'，3'-烯烃。有效地制备了腺嘌呤，次黄嘌呤和2-氨基-6-甲氧基嘌呤2'，3'-二氢-2'，3'-二脱氧核苷（结晶，分析纯产品的总收率为40-60％； 3-5个步骤，通过将5'-O-保护的2'，3'-di-O-甲磺酰基核糖核苷用萘钠处理来将它们合并成一个烧瓶。反应是在环境温度或低于环境温度的条件下使用容易获得的试剂和标准实验室条件进行的。

  DOI：

  10.1021/jo981013m
• 作为产物：
  描述：

  (S)-2-(tert-Butyl-diphenyl-silanyloxymethyl)-5-trimethylsilanyloxy-2,3-dihydro-furan 在 吡啶 、 4-二甲氨基吡啶 、 ammonium sulfate 、 三氟甲磺酸三甲基硅酯 、 氨 、 双氧水 、 二异丁基氢化铝 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 21.75h， 生成 9-[5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-β-D-glycero-pent-2-enofuranosyl]adenine
  参考文献：
  名称：

  A highly stereoselective synthesis of anti-HIV 2',3'-dideoxy- and 2',3'-didehydro-2',3'-dideoxynucleosides

  摘要：

  A general total synthetic method for the stereocontrolled synthesis of 2',3'-dideoxy- as well as 2',3'-didehydro-2',3'-dideoxynucleosides is presented. Introduction of an alpha-phenylselenenyl group at the 2-position of 2,3-dideoxyribosyl acetate directs the glycosyl bond formation to give greater-than-or-equal-to 95% beta-isomer. This 2'-phenylselenenyl nucleoside may be converted to either the 2',3'-dideoxynucleoside by treatment with n-Bu3SnH and Et3B at room temperature or to the unsaturated derivative by treatment with H2O2/cat. pyridine. The application of this method to the syntheses of pyrimidines (ddU, ddT, ddC), 6-substituted purines (ddA, ddI, 6-chloro-ddP, N6-Me-ddA), and 2,6-disubstituted purines (2-F-ddA, 6-chloro-2-amino-ddP) as well as selected 2',3'-didehydro-2',3'-dideoxy derivatives is reported.

  DOI：

  10.1021/jo00040a031

文献信息

• Uracil and adenine nucleosides having a 2′,3′-bromovinyl structure: highly versatile synthons for the synthesis of 2′-C- and 3′-C-Branched 2′,3′-Unsaturated Derivatives
  作者：Kazuhiro Haraguchi、Yoshiharu Itoh、Hiromichi Tanaka、Mitsuhiro Akita、Tadashi Miyasaka

  DOI：10.1016/s0040-4020(01)90190-5

  日期：1993.2

  Preparation of 2′- and 3′-bromo derivatives of 2′,3′-unsaturated uracil and adenine nucleosides has been carried out starting from the corresponding β-hydroxyselenides by way of bromination and successive selenoxide elimination. These compounds have been shown to serve as versatile synthons for the preparation of anti-HIV candidates, 2′-C- and 3′-C-branched 2′,3′-unsaturated nucleosides, through palladium-catalyzed

  从相应的β-羟基硒化物开始，通过溴化和相继的亚硒氧化物消除，已经制备了2'，3'-不饱和尿嘧啶和腺嘌呤核苷的2'-和3'-溴衍生物。这些化合物已显示出可作为通用合成子，可通过钯催化的交叉偶联和卤素-卤代物制备抗HIV候选物，2'-C-和3'-C支链的2'，3'-不饱和核苷。锂交换反应。
• A highly stereoselective synthesis of anti-HIV 2',3'-dideoxy- and 2',3'-didehydro-2',3'-dideoxynucleosides
  作者：J. Warren Beach、Hea O. Kim、Lak S. Jeong、Satyanarayana Nampalli、Qamrul Islam、Soon K. Ahn、J. Ramesh Babu、Chung K. Chu

  DOI：10.1021/jo00040a031

  日期：1992.7

  A general total synthetic method for the stereocontrolled synthesis of 2',3'-dideoxy- as well as 2',3'-didehydro-2',3'-dideoxynucleosides is presented. Introduction of an alpha-phenylselenenyl group at the 2-position of 2,3-dideoxyribosyl acetate directs the glycosyl bond formation to give greater-than-or-equal-to 95% beta-isomer. This 2'-phenylselenenyl nucleoside may be converted to either the 2',3'-dideoxynucleoside by treatment with n-Bu3SnH and Et3B at room temperature or to the unsaturated derivative by treatment with H2O2/cat. pyridine. The application of this method to the syntheses of pyrimidines (ddU, ddT, ddC), 6-substituted purines (ddA, ddI, 6-chloro-ddP, N6-Me-ddA), and 2,6-disubstituted purines (2-F-ddA, 6-chloro-2-amino-ddP) as well as selected 2',3'-didehydro-2',3'-dideoxy derivatives is reported.
• Nucleic Acid Related Compounds. 105. Synthesis of 2‘,3‘-Didehydro-2‘,3‘-dideoxynucleosides from Ribonucleoside Cyclic 2‘,3‘-(Sulfates or Phosphates) or 2‘,3‘-Dimesylates via Reductive Elimination with Sodium Naphthalenide¹
  作者：Morris J. Robins、Elzbieta Lewandowska、Stanislaw F. Wnuk

  DOI：10.1021/jo981013m

  日期：1998.10.1

  gave the 2',3'-unsaturated nucleosides. Parallel treatment of adenosine cyclic 2',3'-phosphate gave the 2',3'-olefin. The adenine, hypoxanthine, and 2-amino-6-methoxypurine 2',3'-didehydro-2',3'-dideoxynucleosides were prepared efficiently (40-60% overall yields of crystalline, analytically pure products; 3-5 steps, some combined into one-flask procedures) by treatment of 5'-O-protected 2',3'-di-O-mesylribonucleosides

  用亚硫酰氟处理嘌呤核糖核苷导致形成环状2'，3'-亚硫酸酯。5'-羟基的乙酰化和Sharpless氧化（NaIO（4）/ RuCl（3））得到环状2'，3'-硫酸酯衍生物。用亚硫酰氯处理5'-O-甲硅烷基保护的核糖核苷，然后氧化，得到了环状2'，3'-硫酸盐的另一种途径。用萘钠（THF / -50℃）还原消除，得到2′，3′-不饱和核苷。腺苷环2'，3'-磷酸的平行处理得到2'，3'-烯烃。有效地制备了腺嘌呤，次黄嘌呤和2-氨基-6-甲氧基嘌呤2'，3'-二氢-2'，3'-二脱氧核苷（结晶，分析纯产品的总收率为40-60％； 3-5个步骤，通过将5'-O-保护的2'，3'-di-O-甲磺酰基核糖核苷用萘钠处理来将它们合并成一个烧瓶。反应是在环境温度或低于环境温度的条件下使用容易获得的试剂和标准实验室条件进行的。