S_P-N⁴-benzoyl-2'-deoxycytidine-3'-O-(2-thio-1,3,2-oxathiaphospholane) | 163616-09-9

• 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: S_P-N⁴-benzoyl-2'-deoxycytidine-3'-O-(2-thio-1,3,2-oxathiaphospholane)
• CAS: 163616-09-9
• 化学式: C₁₈H₂₀N₃O₆PS₂
• 分子量: 469.479
• InChiKey: CCWRHTBHEIIBOY-KWLIWJERSA-N

反应信息

• 作为反应物：
  描述：

  S_P-N⁴-benzoyl-2'-deoxycytidine-3'-O-(2-thio-1,3,2-oxathiaphospholane) 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 0.08h， 生成 N-[1-((2S,4aR,6R,7aS)-2-Mercapto-2-oxo-tetrahydro-2λ⁵-furo[3,2-d][1,3,2]dioxaphosphinin-6-yl)-2-oxo-1,2-dihydro-pyrimidin-4-yl]-benzamide
  参考文献：
  名称：

  Cyclization versus oligomerization of SP- and RP-5′-OH-N4-benzoyl-2′-deoxycytidine-3′-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane)s

  摘要：

  The S-p-isomer of 5 '-OH-N-4-benzoyl-2 '-deoxycytidine-3 '-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane) undergoes DBU-promoted intramolecular cyclization providing as a sole product Sp-deoxycytidine cyclic 3 ',5 '-O,O-phosphorothioate. Unexpectedly, the Rp-counterpart yields a mixture of products consisting of Rp-deoxycytidine cyclic 3 ',5 '-O,O-phosphorothioate and macrocyclic oligo(deoxycytidine phosphorothioate)s. The results of molecular modeling indicate that the dychotomy observed for the R-p substrate may result from remarkably higher energy of the corresponding transition states, caused by the presence of bulky 'spiro' pentamethylene substituent at the position C4 in the oxathiaphospholane ring. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.12.022
• 作为产物：
  描述：

  5′-O-(4,4′-Dimethoxytrityl)-N⁴-benzoyl-2′-deoxycytidine-3′-O-(2-thio-1,3,2-oxathiaphospholane) 在 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.67h， 以53%的产率得到S_P-N⁴-benzoyl-2'-deoxycytidine-3'-O-(2-thio-1,3,2-oxathiaphospholane)
  参考文献：
  名称：

  Cyclization versus oligomerization of SP- and RP-5′-OH-N4-benzoyl-2′-deoxycytidine-3′-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane)s

  摘要：

  The S-p-isomer of 5 '-OH-N-4-benzoyl-2 '-deoxycytidine-3 '-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane) undergoes DBU-promoted intramolecular cyclization providing as a sole product Sp-deoxycytidine cyclic 3 ',5 '-O,O-phosphorothioate. Unexpectedly, the Rp-counterpart yields a mixture of products consisting of Rp-deoxycytidine cyclic 3 ',5 '-O,O-phosphorothioate and macrocyclic oligo(deoxycytidine phosphorothioate)s. The results of molecular modeling indicate that the dychotomy observed for the R-p substrate may result from remarkably higher energy of the corresponding transition states, caused by the presence of bulky 'spiro' pentamethylene substituent at the position C4 in the oxathiaphospholane ring. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.12.022