1,3-O-benzylidene D-erythrulose 4-(t-butyldimethylsilyl) ether | 652979-94-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: 1,3-O-benzylidene D-erythrulose 4-(t-butyldimethylsilyl) ether
• 英文别名: 1,3-O-benzylidene-D-erythrulose 4-(t-butyldimethylsilyl) ether；(2S,4R)-4-[[tert-butyl(dimethyl)silyl]oxymethyl]-2-phenyl-1,3-dioxan-5-one
• CAS: 652979-94-7
• 化学式: C₁₇H₂₆O₄Si
• 分子量: 322.477
• InChiKey: HMDZTKMKKIZOID-CVEARBPZSA-N

物化性质

• 沸点：
  389.1±42.0 °C(Predicted)
• 密度：
  1.035±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.69
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,3-O-benzylidene D-erythrulose 4-(t-butyldimethylsilyl) ether 在 四氮唑 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.28h， 生成 1,3-O-benzylidene-2-C-methyl-D-erythritol 2,4-bis(dibenzylphosphate)
  参考文献：
  名称：

  Synthesis of Enantiopure 2-C-Methyl-d-erythritol 4-Phosphate and 2,4-Cyclodiphosphate from d-Arabitol

  摘要：

  Two key intermediates of the newly discovered mevalonate-independent pathway for isoprenoid biosynthesis were prepared. Optically pure 2-C-methyl-D-erythritol 4-phosphate and 2,4-cyclodiphosphate were chemically synthesized from D-arabitol using a convenient benzylidene and tert-butyldimethylsilyl protection of polyhydroxylated intermediates. The new scheme offers a straightforward route to analogues and labeled forms.

  DOI：

  10.1021/ol0362562
• 作为产物：
  描述：

  2,4-O-benzylidene-D-threose 在 ruthenium(IV) oxide 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 sodium periodate 、 苄基三乙基氯化铵 、 potassium carbonate 、 三乙胺 作用下， 以 甲醇 、 四氯化碳 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 17.17h， 生成 1,3-O-benzylidene D-erythrulose 4-(t-butyldimethylsilyl) ether
  参考文献：
  名称：

  Synthesis of Enantiopure 2-C-Methyl-d-erythritol 4-Phosphate and 2,4-Cyclodiphosphate from d-Arabitol

  摘要：

  Two key intermediates of the newly discovered mevalonate-independent pathway for isoprenoid biosynthesis were prepared. Optically pure 2-C-methyl-D-erythritol 4-phosphate and 2,4-cyclodiphosphate were chemically synthesized from D-arabitol using a convenient benzylidene and tert-butyldimethylsilyl protection of polyhydroxylated intermediates. The new scheme offers a straightforward route to analogues and labeled forms.

  DOI：

  10.1021/ol0362562

文献信息

• The Dioxanone Approach to (2<i>S</i>,3<i>R</i>)-2-<i>C</i>-Methylerythritol 4-Phosphate and 2,4-Cyclodiphosphate, and Various MEP Analogues
  作者：Chandraiah Lagisetti、Marek Urbansky、Robert M. Coates

  DOI：10.1021/jo0711900

  日期：2007.12.1

  epoxide of (2S,4R)-4-tert-butyldimethylsilyloxymethyl-5-methylene-2-phenyl-1,3-dioxane, primary-selective phosphorylation, and cleavage of the silyl, benzylidene, and benzyl protecting groups. Regioselective cleavage of the acetal ring of 1,3-benzylidene 2-C-methylerythritol silyl ether by ozonolysis afforded a 1,2,3-triol 3-monobenzoate intermediate that was converted to the novel amino sugar, 1-amino-1

  所述的高效合成非甲羟戊酸途径的中间体2- Ç -methylerythritol 4-磷酸（MEP）和2- Ç -methylerythritol 2,4-环（ME-2,4- cycloPP），以及母体四醇2- Ç报道了对映体纯的来自（2 S，4 R）-顺式-2-苯基-4-叔丁基二甲基甲硅烷氧基-1,3-二恶烷-5-酮的-甲基赤藓糖醇。通过高度轴向选择性添加CH 3来安装C-甲基的2 S构型MgBr（20：1）为手性二恶烷酮羰基。初级选择性单磷酸化和2,4-双磷酸化，然后进行脱硅和氢解反应生成游离的单磷酸和二磷酸，在后一种情况下，环化形成八元磷酸酐，得到MEP和ME-2 ，4-环PP产率高。通过LiAlH 4还原（2 S，4 R）-4-叔丁基二甲基甲硅烷基氧基甲基-5-亚甲基-2-苯基的顺式，顺式环氧化物，可得到C2异构体类似物2- C-甲基苏糖醇及其4-磷酸酯。-1,3-二恶烷，一级选择
• Irreversible Inhibition of IspG, a Target for the Development of New Antimicrobials, by a 2‐Vinyl Analogue of its MEcPP Substrate
  作者：Vivien Herrscher、Clea Witjaksono、Marie Buchotte、Claire Ferret、Fabien Massicot、Jean‐Luc Vasse、Franck Borel、Jean‐Bernard Behr、Myriam Seemann

  DOI：10.1002/chem.202200241

  日期：2022.5.25

  the aim of providing new reactive centers to be covalently trapped by neighboring amino acid residues. The synthesized substrate analogue displayed irreversible inhibition towards IspG. Furthermore, we have shown that electron transfer occurs prior to inhibition; this might designate conjugated intermediates as probable affinity tags through covalent interaction at the catalytic site. This is the first

  IspG（也称为 GcpE）是一种氧敏感的 [4Fe-4S] 酶，可催化磷酸甲基赤藓糖醇 (MEP) 途径的倒数第二步，这是药物开发的经过验证的目标。它将 2-C-甲基-d-赤藓糖醇-2,4-环二磷酸 (MEcPP) 转化为 (E)-4-羟基-3-甲基-丁-2-烯基-1-二磷酸 (HMBPP)。该反应同化为还原性脱水，涉及氧化还原伙伴，负责将两个电子正式转移到底物 MEcPP。MEcPP 的 2-乙烯基类似物旨在在酶催化过程中产生共轭物种，目的是提供新的反应中心以被相邻的氨基酸残基共价捕获。合成的底物类似物对 IspG 表现出不可逆的抑制作用。此外，我们已经证明电子转移发生在抑制之前。这可能通过催化位点的共价相互作用将共轭中间体指定为可能的亲和标签。这是 IspG 金属酶不可逆抑制剂的首次报道。
• Synthesis of Methylerythritol Phosphate Analogues and Their Evaluation as Alternate Substrates for IspDF and IspE from <i>Agrobacterium tumefaciens</i>
  作者：Sergiy G. Krasutsky、Marek Urbansky、Chad E. Davis、Christian Lherbet、Robert M. Coates、C. Dale Poulter

  DOI：10.1021/jo501529k

  日期：2014.10.3

  The methylerythritol phosphate biosynthetic pathway, found in most Bacteria, some parasitic protists, and plant chloroplasts, converts D-glyceraldehyde phosphate and pyruvate to isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP), where it intersects with the mevalonate pathway found in some Bacteria, Archaea, and Eukarya, including the cytosol of plants. D-3-Methylerythritol-4-phosphate (MEP), the first pathway-specific intermediate in the pathway, is converted to IPP and DMAPP by the consecutive action of the IspD-H proteins. We synthesized five D-MEP analogues-D-erythritol-4-phosphate (EP), D-3-methylthrietol-4-phosphate (MTP), D-3-ethylerythritol-4-phosphate (EEP), D-1-amino-3-methylerythritol-4-phosphate (NMEP), and D-3-methylerythritol-4-thiolophosphate (MESP)-and studied their ability to function as alternative substrates for the reactions catalyzed by the IspDF fusion and IspE proteins from Agrobacterium tumefaciens, which covert MEP to the corresponding eight-membered cyclic diphosphate. All of the analogues, except MTP, and their products were substrates for the three consecutive enzymes.