5'-O-(4-Monomethoxytrityl)-3'-nitro-2',3'-dideoxy-2',3'-didehydrothymidine | 148279-88-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 5'-O-(4-Monomethoxytrityl)-3'-nitro-2',3'-dideoxy-2',3'-didehydrothymidine
• 英文别名: 2',3'-dideoxy-2',3'-didehydro-3'-nitrothymidine；1-[(2R,5S)-5-[[(4-methoxyphenyl)-diphenylmethoxy]methyl]-4-nitro-2,5-dihydrofuran-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 148279-88-3
• 化学式: C₃₀H₂₇N₃O₇
• 分子量: 541.56
• InChiKey: NTXDUFHUUUNKEE-KAYWLYCHSA-N

物化性质

• 密度：
  1.38±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  40
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  123
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5'-O-(4-Monomethoxytrityl)-3'-nitro-2',3'-dideoxy-2',3'-didehydrothymidine 在 四丁基氟化铵 、 四甲基胍 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 0.5h， 生成 1-<5-O-(MMTr)-2,3-dideoxy-2-(R)-thiophenyl-3-(S)-(β-cyanoethyl)-3-nitro-β-D-pentofuranosyl>thymine
  参考文献：
  名称：

  2'，3'-dideoxy-2'，3'-didehydro-3'-取代的胸苷的新合成

  摘要：

  苯硫醚酸根阴离子与2'，3'-二脱氧-2'，3'-二氢-2'-硝基胸苷1的迈克尔加成反应，以及随后在C-3'处与各种电子不足的试剂（如甲醛，甲基乙烯基酮）的亨利反应丙烯腈产生了1-（2，3-二脱氧-3-取代的-2-硫代苯基-3-硝基-β-D-戊呋喃糖基）胸腺嘧啶4 – 12 [α-取代（主要）的各种非对映异构体混合物；β-取代（次要）]，收率为29–82％。在该反应中形成的产物的立体化学清楚地表明，在非对映异构体的C3'处生成的碳负离子（1.3：1的比例，1H-NMR）优先从戊呋喃糖环的α面攻击缺电子试剂。随后，来自-3'-硝基和2'-苯硫基4，5，8和11处理时被消除与卜3 SNH和AIBN，得到2'，3'-二脱氧-2'，3'-二脱氢-3- ' -取代的胸苷13 - 18中79-85％的产率。本文详细介绍的结果代表了2'，3'-dideoxy-2'，3'-didehydro-3'-的简便

  DOI：

  10.1016/s0040-4020(01)80201-5
• 作为产物：
  描述：

  丁烯酮 、 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以29%的产率得到1-<5-O-(MMTr)-2,3-dideoxy-2-(R)-thiophenyl-3-(S)-(3-oxobutyl)-3-nitro-β-D-pentofuranosyl>thymine
  参考文献：
  名称：

  2'，3'-dideoxy-2'，3'-didehydro-3'-取代的胸苷的新合成

  摘要：

  苯硫醚酸根阴离子与2'，3'-二脱氧-2'，3'-二氢-2'-硝基胸苷1的迈克尔加成反应，以及随后在C-3'处与各种电子不足的试剂（如甲醛，甲基乙烯基酮）的亨利反应丙烯腈产生了1-（2，3-二脱氧-3-取代的-2-硫代苯基-3-硝基-β-D-戊呋喃糖基）胸腺嘧啶4 – 12 [α-取代（主要）的各种非对映异构体混合物；β-取代（次要）]，收率为29–82％。在该反应中形成的产物的立体化学清楚地表明，在非对映异构体的C3'处生成的碳负离子（1.3：1的比例，1H-NMR）优先从戊呋喃糖环的α面攻击缺电子试剂。随后，来自-3'-硝基和2'-苯硫基4，5，8和11处理时被消除与卜3 SNH和AIBN，得到2'，3'-二脱氧-2'，3'-二脱氢-3- ' -取代的胸苷13 - 18中79-85％的产率。本文详细介绍的结果代表了2'，3'-dideoxy-2'，3'-didehydro-3'-的简便

  DOI：

  10.1016/s0040-4020(01)80201-5

文献信息

• Diels-alder reaction of 2′,3′-unsaturated-3′-nitro-thymidine. First chemical evidence of nitroxide radical formation in the radical-promoted denitration reaction
  作者：N. Hossain、J. Plavec、C. Thibaudeau、J. Chattopadhyaya

  DOI：10.1016/s0040-4020(01)91224-4

  日期：1993.1

  Diels-Alder reaction of an appropriately functionalized nucleoside [2′,3′-dideoxy-2′,3′-didehydro-3′-nitrothymidine (1)] has been used for the first time as a substrate to yield various unique fused 2′,3′-dideoxy-2′,3′-bis-substituted nucleoside derivatives (2 – 5, 8 – 16) which are not hithertofore available through any other known routes. First unequivocal evidence of the formation of nitroxide radical

  适当功能化的核苷[2'，3'-二脱氧-2'，3'-二氢-3'-硝基胸苷（1）]的狄尔斯-阿尔德反应首次用作底物以产生各种独特的稠合2 '，3'-二脱氧-2'，3'-双-取代的核苷衍生物（2 - 5,8 - 16），其是迄今为止在不可通过任何其它已知的路由。正丁基期间硝基氧自由基的形成的第一明确的证据3 SNH促进脱硝反应已经通过cycloadducts（稠合4H-5,6-二氢-1,2-恶嗪衍生物的分离被还提出6,7，18 ，19）是由于在分子内反应中氮氧化物自由基被烯烃或酮官能团捕获而形成的。
• The synthesis of new 3′-bis--substituted-3′-deoxy-3′-dehydro-[3.3.0]-α-fused thymidines by intramolecular radical trapping by tethered acetylenes
  作者：Neeraj Garg、Nafizal Hossain、Jyoti Chattopadhyaya

  DOI：10.1016/s0040-4020(01)90436-3

  日期：1994.4

  The Michael addition reaction of propargyl alcohol with 3'-nitro-olefin I and subsequent Henry reaction at C-3' with electron deficient reagents has produced various diastereomeric mixtures of 2'-Q-propynyl-3'-deoxy-3- dehydro-3'-C-substituted-3'-nitro-thymidine derivatives 4 - 7 [alpha-substitution (major); beta-substitution (minor)] in 55-80% yield. Subsequently, the intramolecular cyclization-trapping of carbon radicals by tethered acetylene in 4 - 7 by the treatment with Bu(3)SnH and AIBN afforded 3'-bis-C-substituted-[3.3.0]-cis-fused thymidines 8 - 11 in 86-90% yield. The results detailed here represent the first examples of title compounds using a three-step procedure: (1) Michael addition of the propargyl alcohol to nitro-olefin, (2) Henry reaction with electron-deficient reagents, and (3) subsequent inramolecular cyclization-trapping of tertiary carbon radicals by a tethered acetylene.
• [4 + 2] and [3 + 2] Cycloaddition reactions of 2',3'-dideoxy-3'-nitro-2',3'-didehydrothymidine with ethyl vinyl ether
  作者：Alexander Papchikhin、Peter Agback、Janez Plavec、Jyoti Chattopadhyaya

  DOI：10.1021/jo00062a036

  日期：1993.5

  Cycloaddition reaction of 1-(5'-O-(monomethoxytrityl)-2',3'-dideoxy-3'-nitro-beta-D-glycero-pent-2'-enofuranosyl)thymine (1a) with ethyl vinyl ether gave a diastereomeric mixture of [3.4.0]sugar-fused bicyclic (2a) (27%) and (3) (12%) and the tricyclic (4a) (47%) derivatives. An identical reaction with (2',3'-dideoxy-3'-nitro-beta-D-glycero-pent-2'-enofuranosyl)thymine (1b) gave only bicyclic 2b (40%) and tricyclic 4b (43%) in a stereospecific manner. Chemical evidence has been presented which suggests that only one of the diastereomeric nitronates (i.e., 2a) formed as a result of [4 + 2] addition reaction across a 4pi heterodiene system undergoes the second [3 + 2] cycloaddition reaction across its nitronate function by a second molecule of the reagent to give the tricyclic product 4a. The configurations of new chiral centers have been assigned as C2'-R/C8-R in 2a and 2b, C2'-R/C8-S in 3, and C2'-R/C3'-S/C8-R/C12-S in 4a and 4b by detailed 500-MHz NMR studies. Detailed analysis Of 3J(HH) coupling constants at 500 MHz and estimation of interproton distances by 1D H-1 difference NOE and the NOESY spectra have enabled us to define the conformation of novel thymidine derivatives 2b, 3, and 4b: (i) The pentose sugars in 2b and 3 are 2'-endo-3'-exo (P = 142-degrees, PSI(m) = 34-degrees for 2b and P = 140-degrees, PSI(m) = 33-degrees for 3), and the constituent six-membered ring are in the half-chair/half-boat conformation. (ii) For tricyclic nucleoside 4b, the pentose sugar moiety adopts 2'-endo conformation (P = 161-degrees, PSI(m) = 40-degrees) with the fused six-membered ring in 09C(C2'), conformation, whereas the conformation of its fused-spiro isoxazolidine ring can be described by P = 188-degrees, PSI(m) = 40-degrees.
• New synthesis of 2′, 3′-dideoxy-2′, 3′-didehydro-3′--substituted thymidines
  作者：Nafizal Hossain、Neeraj Garg、Jyoti Chattopadhyaya

  DOI：10.1016/s0040-4020(01)80201-5

  日期：1993.1

  results detailed in this paper represent the first examples of a facile synthesis of 2′,3′-dideoxy-2′,3′-didehydro-3′--branched thymidines using a three-step procedure: (1) Michael addition of the phenylthiolate to nitro-olefin, (2) Henry reaction with electron-deficient reagents, and (3) subsequently, free-radical induced elimination of phenylthio and nitro groups.

  苯硫醚酸根阴离子与2'，3'-二脱氧-2'，3'-二氢-2'-硝基胸苷1的迈克尔加成反应，以及随后在C-3'处与各种电子不足的试剂（如甲醛，甲基乙烯基酮）的亨利反应丙烯腈产生了1-（2，3-二脱氧-3-取代的-2-硫代苯基-3-硝基-β-D-戊呋喃糖基）胸腺嘧啶4 – 12 [α-取代（主要）的各种非对映异构体混合物；β-取代（次要）]，收率为29–82％。在该反应中形成的产物的立体化学清楚地表明，在非对映异构体的C3'处生成的碳负离子（1.3：1的比例，1H-NMR）优先从戊呋喃糖环的α面攻击缺电子试剂。随后，来自-3'-硝基和2'-苯硫基4，5，8和11处理时被消除与卜3 SNH和AIBN，得到2'，3'-二脱氧-2'，3'-二脱氢-3- ' -取代的胸苷13 - 18中79-85％的产率。本文详细介绍的结果代表了2'，3'-dideoxy-2'，3'-didehydro-3'-的简便