O,O,O',S-tetrakis(trimethylsilyl) thiodiphosphate | 289718-26-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: O,O,O',S-tetrakis(trimethylsilyl) thiodiphosphate
• 英文别名: tetra-(trimethylsilanyl)thiolodiphosphate；Thiodiphosphoric acid ((HO)2P(O)OP(O)(OH)(SH)), tetrakis(trimethylsilyl) ester；bis(trimethylsilyl) [trimethylsilyloxy(trimethylsilylsulfanyl)phosphoryl] phosphate
• CAS: 289718-26-9
• 化学式: C₁₂H₃₆O₆P₂SSi₄
• 分子量: 482.77
• InChiKey: TYCYSIKDMLODTG-UHFFFAOYSA-N

物化性质

• 沸点：
  396.6±25.0 °C(Predicted)
• 密度：
  1.055±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.34
• 重原子数：
  25
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  96.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  四丁基氢氧化铵 、 O,O,O',S-tetrakis(trimethylsilyl) thiodiphosphate 以 水 、 乙腈 为溶剂， 以88%的产率得到tris(tetra-n-butylammonium) thiodiphosphate
  参考文献：
  名称：

  了解并改造葎草烯合酶的立体选择性

  摘要：

  非经典萜烯环化酶 AsR6 负责在托酚酮倍半萜 (TS) 异戊烯 A 生物合成过程中形成 2 E ,6 E ,9 E -葎草烯。未配体 AsR6 和与晶体复合的 AsR6 的结构环化反应产物和硫代二磷酸揭示了一个新的法呢基二磷酸结合基序，该基序包含独特的双核 Mg 2+簇和重要的 K289 残基，该残基在参与 TS 形成的所有葎草烯合酶中都是保守的。AsR6 及其同源物 EupR3 的基于结构的定点诱变鉴定出单个残基 L285/M261，其控制 2 E ,6 E ,9 E - 或 2 Z ,6 E ,9 E -humulene的产生。使用不同的类异戊二烯前体研究了观察到的立体选择性的可能机制，结果表明 M261 对产物形成具有把关控制作用。

  DOI：

  10.1002/anie.202106718
• 作为产物：
  描述：

  碘代三甲硅烷 在 四甲基焦磷酸硫代酸酯 作用下， 反应 6.0h， 生成 O,O,O',S-tetrakis(trimethylsilyl) thiodiphosphate
  参考文献：
  名称：

  Synthesis of (S)-Isoprenoid Thiodiphosphates as Substrates and Inhibitors

  摘要：

  Thiolo thiophosphate analogues of isopentenyl diphosphate (IPP), dimethylallyl. diphosphate (DMAPP), geranyl diphosphate (GPP), farnesyl diphosphate (FPP), and geranylgeranyl diphosphate (GGPP) were synthesized, Inorganic thiopyrophosphate (SPP) was prepared from trimethyl phosphate in four steps. The tris(tetra-n-butylammonium) salt was then used to convert isopentenyl tosylate to (S)-isopentenyl thiodiphosphate (ISPP). (S)-Dimethylallyl (DMASPP), (S)-geranyl (GSPP), (S)-farnesyl (FSPP), and (S)-geranylgeranyl thiodiphosphate (GGSPP) were prepared from the corresponding bromides in a similar manner. ISPP and GSPP were substrates for avian farnesyl diphosphate synthase (FPPase). Incubation of the enzyme with ISPP and GPP gave FSPP, whereas incubation with IPP and GSPP gave FPP. GSPP was a substantially less reactive than GPP in the chain elongation reaction and was an excellent competitive inhibitor, K-I(GSPP) = 24.8 muM, of the enzyme. Thus, when ISPP and DMAPP were incubated with FPPase, GSPP accumulated and was only slowly converted to FSPP.

  DOI：

  10.1021/jo010505n
• 作为试剂：
  描述：

  四丁基氢氧化铵 在 O,O,O',S-tetrakis(trimethylsilyl) thiodiphosphate 作用下， 以 水 、 乙腈 为溶剂， 以5.36 g的产率得到tris-(tetra-n-butylammonium)thiolodiphosphate
  参考文献：
  名称：

  Synthesis of (S)-Isoprenoid Thiodiphosphates as Substrates and Inhibitors

  摘要：

  Thiolo thiophosphate analogues of isopentenyl diphosphate (IPP), dimethylallyl. diphosphate (DMAPP), geranyl diphosphate (GPP), farnesyl diphosphate (FPP), and geranylgeranyl diphosphate (GGPP) were synthesized, Inorganic thiopyrophosphate (SPP) was prepared from trimethyl phosphate in four steps. The tris(tetra-n-butylammonium) salt was then used to convert isopentenyl tosylate to (S)-isopentenyl thiodiphosphate (ISPP). (S)-Dimethylallyl (DMASPP), (S)-geranyl (GSPP), (S)-farnesyl (FSPP), and (S)-geranylgeranyl thiodiphosphate (GGSPP) were prepared from the corresponding bromides in a similar manner. ISPP and GSPP were substrates for avian farnesyl diphosphate synthase (FPPase). Incubation of the enzyme with ISPP and GPP gave FSPP, whereas incubation with IPP and GSPP gave FPP. GSPP was a substantially less reactive than GPP in the chain elongation reaction and was an excellent competitive inhibitor, K-I(GSPP) = 24.8 muM, of the enzyme. Thus, when ISPP and DMAPP were incubated with FPPase, GSPP accumulated and was only slowly converted to FSPP.

  DOI：

  10.1021/jo010505n

文献信息

• Synthesis of Geranyl <i>S</i>-Thiolodiphosphate. A New Alternative Substrate/Inhibitor for Prenyltransferases
  作者：Richard M. Phan、C. Dale Poulter

  DOI：10.1021/ol006055n

  日期：2000.7.1

  [GRAPHICS]The tris(tetra-n-butylammonium) salt of thiopyrophosphate 5 was prepared from trimethyl phosphate in four steps. Treatment of geranyl bromide with 5 gave an 80% yield of geranyl S-thiolodiphosphate (6), Thiolodiphosphate 6 is substantially less reactive than geranyl diphosphate (7) in the prenyl transfer reaction catalyzed by farnesyl diphosphate synthase and is a good inhibitor of the enzyme.
• Synthesis of (<i>S</i>)-Isoprenoid Thiodiphosphates as Substrates and Inhibitors
  作者：Richard M. Phan、C. Dale Poulter

  DOI：10.1021/jo010505n

  日期：2001.10.1

  Thiolo thiophosphate analogues of isopentenyl diphosphate (IPP), dimethylallyl. diphosphate (DMAPP), geranyl diphosphate (GPP), farnesyl diphosphate (FPP), and geranylgeranyl diphosphate (GGPP) were synthesized, Inorganic thiopyrophosphate (SPP) was prepared from trimethyl phosphate in four steps. The tris(tetra-n-butylammonium) salt was then used to convert isopentenyl tosylate to (S)-isopentenyl thiodiphosphate (ISPP). (S)-Dimethylallyl (DMASPP), (S)-geranyl (GSPP), (S)-farnesyl (FSPP), and (S)-geranylgeranyl thiodiphosphate (GGSPP) were prepared from the corresponding bromides in a similar manner. ISPP and GSPP were substrates for avian farnesyl diphosphate synthase (FPPase). Incubation of the enzyme with ISPP and GPP gave FSPP, whereas incubation with IPP and GSPP gave FPP. GSPP was a substantially less reactive than GPP in the chain elongation reaction and was an excellent competitive inhibitor, K-I(GSPP) = 24.8 muM, of the enzyme. Thus, when ISPP and DMAPP were incubated with FPPase, GSPP accumulated and was only slowly converted to FSPP.
• Understanding and Engineering the Stereoselectivity of Humulene Synthase
  作者：Carsten Schotte、Peer Lukat、Adrian Deuschmann、Wulf Blankenfeldt、Russell J. Cox

  DOI：10.1002/anie.202106718

  日期：2021.9.6

  cyclized reaction product and thiolodiphosphate reveal a new farnesyl diphosphate binding motif that comprises a unique binuclear Mg2+-cluster and an essential K289 residue that is conserved in all humulene synthases involved in TS formation. Structure-based site-directed mutagenesis of AsR6 and its homologue EupR3 identify a single residue, L285/M261, that controls the production of either 2E,6E,9E-

  非经典萜烯环化酶 AsR6 负责在托酚酮倍半萜 (TS) 异戊烯 A 生物合成过程中形成 2 E ,6 E ,9 E -葎草烯。未配体 AsR6 和与晶体复合的 AsR6 的结构环化反应产物和硫代二磷酸揭示了一个新的法呢基二磷酸结合基序，该基序包含独特的双核 Mg 2+簇和重要的 K289 残基，该残基在参与 TS 形成的所有葎草烯合酶中都是保守的。AsR6 及其同源物 EupR3 的基于结构的定点诱变鉴定出单个残基 L285/M261，其控制 2 E ,6 E ,9 E - 或 2 Z ,6 E ,9 E -humulene的产生。使用不同的类异戊二烯前体研究了观察到的立体选择性的可能机制，结果表明 M261 对产物形成具有把关控制作用。