Trifluoro-methanesulfonic acid (3aR,4S,6R,6aR)-6-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxymethyl]-2,2-dimethyl-tetrahydro-cyclopenta[1,3]dioxol-4-yl ester | 189574-99-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: Trifluoro-methanesulfonic acid (3aR,4S,6R,6aR)-6-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxymethyl]-2,2-dimethyl-tetrahydro-cyclopenta[1,3]dioxol-4-yl ester
• 英文别名: [(3aR,4S,6R,6aR)-6-[[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-4,5,6,6a-tetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl] trifluoromethanesulfonate
• CAS: 189574-99-0
• 化学式: C₁₈H₃₃F₃O₆SSi
• 分子量: 462.603
• InChiKey: BVJXOWWKTGTEIO-BARDWOONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.42
• 重原子数：
  29.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  Trifluoro-methanesulfonic acid (3aR,4S,6R,6aR)-6-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxymethyl]-2,2-dimethyl-tetrahydro-cyclopenta[1,3]dioxol-4-yl ester 在 四丁基氟化铵 、 potassium carbonate 作用下， 以 乙二醇二甲醚 为溶剂， 生成 8-Bromo-1-((3aS,4R,6R,6aR)-6-hydroxymethyl-2,2-dimethyl-tetrahydro-cyclopenta[1,3]dioxol-4-yl)-9-((3aR,4R,6R,6aR)-6-hydroxymethyl-2,2-dimethyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-yl)-1,9-dihydro-purin-6-one
  参考文献：
  名称：

  细胞内Ca（2+）动员腺嘌呤核苷酸。腺苷A的环状ADP-碳环核糖和C-糖苷类似物的合成及其生物学活性。

  摘要：

  我们设计了新颖的Ca（2+）动员嘌呤核苷酸，环ADP-碳环核糖4，其肌苷同源物5和C-糖苷腺苷A6。在合成cADPR类似物时，分子内缩合形成焦磷酸酯键应为关键步骤。我们开发了一种通过用I2或AgNO3活化苯硫代磷酸酯基团来形成分子内焦磷酸酯键的有效方法。使用该方法，我们合成了目标化合物4和5。使用暂时的硅链自由基偶联反应来构建（3'alpha，1“ alpha）-C，可以合成腺磷素A的C-糖苷类似物6。 -糖苷结构为关键步骤。

  DOI：

  10.1081/ncn-100002320
• 作为产物：
  描述：

  Acetic acid (3aS,4R,6R,6aR)-6-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxymethyl]-2,2-dimethyl-tetrahydro-cyclopenta[1,3]dioxol-4-yl ester 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 重铬酸吡啶 、 4 A molecular sieve 、 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 Trifluoro-methanesulfonic acid (3aR,4S,6R,6aR)-6-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxymethyl]-2,2-dimethyl-tetrahydro-cyclopenta[1,3]dioxol-4-yl ester
  参考文献：
  名称：

  Nucleosides and Nucleotides. 173. Synthesis of Cyclic IDP-carbocyclic-ribose, a Stable Mimic of Cyclic ADP-ribose. Significant Facilitation of the Intramolecular Condensation Reaction of N-1-(Carbocyclic-ribosyl)inosine 5‘,6‘‘-Diphosphate Derivatives by an 8-Bromo-Substitution at the Hypoxanthine Moiety

  摘要：

  Cyclic ADP-ribose (cADPR, 1) is a general mediator involved in cellular Ca2+ signaling. However, both the biological and chemical instability of cADPR limit studies on its physiological role. We designed cyclic ADP-carbocyclic-ribose (3) and its inosine congener 4 as stable mimics of cADPR and successfully synthesized 4. Starting with cyclopentadiene, the optically active carbocyclic unit 8 was constructed via enzymatic optical resolution. S(N)2 reactions of 8 with inosine derivative 7 and the 8-bromoinosine derivative 25 gave the N-1-substituted derivatives 6 and 26, which were converted to the corresponding diphosphate derivatives 5 and 22. The intramolecular condensation reactions between the two phosphate groups of 5 and 22 were investigated, Although the reaction with inosine derivative 5 did not produce any of the cyclization product 20, treatment of the corresponding 8-bromoinosine derivative 22 with EDC gave the desired intramolecular condensation product 29 in 23% yield. Thus, the significant effect of the 8-bromo group at the hypoxanthine moiety in facilitating the key intramolecular condensation reaction between the phosphate groups of the substrate 22 was recognized. This is possibly due to conformational restriction of the molecule in a syn-form around its glycosyl linkage. The 8-bromo and isopropylidene groups were removed in succession to give the target compound 4. This is the first total synthesis of this type of cyclic nucleotide.

  DOI：

  10.1021/jo9717797

文献信息

• Nucleosides and Nucleotides. 192. Toward the Total Synthesis of Cyclic ADP-Carbocyclic-Ribose. Formation of the Intramolecular Pyrophosphate Linkage by a Conformation-Restriction Strategy in a<i>Syn</i>-form Using a Halogen Substitution at the 8-Position of the Adenine Ring
  作者：Yuji Sumita、Michiyo Shirato、Yoshihito Ueno、Akira Matsuda、Satoshi Shuto

  DOI：10.1080/15257770008033002

  日期：2000.1

  8-bromo-N6-trichloroacetyl-2',3'-O-isopropylideneadenosine 9c gave N-1-carbocyclic derivative, which was deprotected to give 5'-5"-diol derivatives 18. When 18 was treated with POCl3 in PO(OEt)3, the bromo group at the 8-position was replaced to give N-1-carbocyclic-8-chloroadenosine 5',5"-diphosphate derivative 19 in 43% yield. Treatment of 19 with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride gave the

  研究了作为环状ADP-核糖的稳定模拟物的环状ADP-碳环-核糖（2）的合成。通过缩合19的两个磷酸基团，成功实现了18元骨架结构的构建，这可能是由于在腺嘌呤部分使用8-氯取代基限制了顺式底物构象的缘故。通过先前开发的方法构建的旋光碳环单元8与8-溴-N6-三氯乙酰基-2'，3'-O-异丙基亚氨腺苷9c之间的SN2反应生成N-1-碳环衍生物，将其脱保护为产生5′-5″-二醇衍生物18。当在PO（OEt）3中用POCl 3处理18时，在8位上的溴基被取代，得到N-1-碳环-8-氯腺苷5′，5″。 -二磷酸酯衍生物19，产率43％。用1-（3-二甲基氨基丙基）-3-乙基碳二亚胺盐酸盐处理19，以10％的产率得到所需的分子内缩合产物20。这是包含cADPR相关化合物与腺嘌呤碱基的分子内焦磷酸键的18元骨架结构的第一个化学结构。
• Alternative synthesis of cyclic IDP-carbocyclic ribose. Efficient cyclization of an 8-bromo-N1-[5-(phosphoryl)carbocyclic-ribosyl]inosine 5′-phenylthiophosphate derivative mediated by iodine
  作者：Masayoshi Fukuoka、Satoshi Shuto、Noriaki Minakawa、Yoshihito Ueno、Akira Matsuda

  DOI：10.1016/s0040-4039(99)00977-6

  日期：1999.7

  An efficient synthesis of cyclic IDP-carbocyclic-ribose, as a stable mimic for cyclic ADP-ribose, was achieved. N-1-Carbocyclic-ribosylinosine derivative 15, prepared from N-1-(2,4-dinitrophenyl)inosine derivative 10 and an optically active carbocyclic amine 11, was converted to 8-bromo-N-1-carbocyclic-ribosylinosine bis-phosphate derivative 20. Treatment of 20 with I-2 in the presence of molecular sieves in pyridine gave the desired cyclic product 8 quantitatively, which was deprotected and reductively debrominated to give the target cyclic IDP-carbocyclic ribose (3). (C) 1999 Elsevier Science Ltd. All rights reserved.