(2R,4aR,6S,7R,8aS)-6-Hydroxymethyl-6-methyl-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-ol | 312308-11-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: (2R,4aR,6S,7R,8aS)-6-Hydroxymethyl-6-methyl-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-ol
• 英文别名: (2R,4aR,6S,7R,8aS)-6-(hydroxymethyl)-6-methyl-2-phenyl-4a,7,8,8a-tetrahydro-4H-pyrano[3,2-d][1,3]dioxin-7-ol
• CAS: 312308-11-5
• 化学式: C₁₅H₂₀O₅
• 分子量: 280.321
• InChiKey: FRTSSENBPVTHPW-JARUQAPTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  68.2
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,4aR,6S,7R,8aS)-6-Hydroxymethyl-6-methyl-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-ol 在 palladium dihydroxide 、 camphor-10-sulfonic acid 2,6-二甲基吡啶 、 Grubbs catalyst first generation 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 MS-4 Angstroem 、 四丁基氟化铵 、 氢气 、 sodium hexamethyldisilazane 、 sodium hydride 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 二氯甲烷 、 二甲基亚砜 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 生成 [(2S,3R,4aS,8aR)-3-(tert-Butyl-dimethyl-silanyloxy)-2,8-dimethyl-2,3,4,4a,6,8a-hexahydro-pyrano[3,2-b]pyran-2-yl]-acetonitrile
  参考文献：
  名称：

  brevetoxin-B的合成研究。第1部分：ABC环系统的立体选择性合成

  摘要：

  短裸-B的ABC-环系统基于所述6-被立体选择性地合成的内切羟基methylepoxide，闭环烯烃复分解和SMI的环化2诱导的还原性分子内环化。

  DOI：

  10.1016/s0040-4039(00)01341-1
• 作为产物：
  描述：

  (2R,4S,5R)-4-[[(2R,3R)-3-(hydroxymethyl)-3-methyloxiran-2-yl]methyl]-2-phenyl-1,3-dioxan-5-ol 在 4-甲基苯磺酸吡啶 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到(2R,4aR,6S,7R,8aS)-6-Hydroxymethyl-6-methyl-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-ol
  参考文献：
  名称：

  麦托毒素的C'D'E'F'-环系统和冈比亚醇的FG-环系统的立体选择性合成。

  摘要：

  [结构：见文字]。麦托毒素的C'D'E'F'环系统和冈比亚醇的FG环系统完成了立体选择性合成。关键步骤包括甲基环氧化物的6-内环化，SmI2诱导的还原环化，乙烯基环氧化合物的6-内环化以及内酯环的形成。

  DOI：

  10.1021/ol016355k

文献信息

• Stereoselective Synthesis of 2,6-<i>syn</i>-Dimethyl-tetrahydropyran Derivatives, Important Segments of Marine Polycyclic Ethers, by Unique Insertion of the Methyl Group
  作者：Michihiro Maemoto、Atsushi Kimishima、Tadashi Nakata

  DOI：10.1021/ol9018419

  日期：2009.11.5

  have a 1′-mesyloxy group at the C2-side chain, with Me3Al effected stereoselective insertion of a methyl group at the C2-position to give 2,6-syn-dimethyl-tetrahydropyran derivatives. This reaction proceeds via removal of the mesyloxy group, 1,2-hydride shift, and stereoselective insertion of a methyl group into the resulting oxonium ion.

  用Me 3 Al处理在C2-侧链上具有1'-甲氧基的6-甲基-四氢吡喃衍生物，实现了在C2-位上甲基的立体选择性插入，从而得到2,6-顺-二甲基-四氢吡喃衍生物。该反应通过除去甲磺酰氧基，1，2-氢化物移位以及将甲基立体选择性地插入所得的氧鎓离子中而进行。
• Synthetic Studies on Maitotoxin. 3. Stereoselective Synthesis of the BCDE-Ring System
  作者：Masanori Satoh、Hiroyuki Koshino、Tadashi Nakata

  DOI：10.1021/ol8002699

  日期：2008.5.1

  The stereoselective synthesis of the BCDE-ring system of maitotoxin has been accomplished through a two-directional strategy for the construction of polycyclic ether. The key reactions involve SmI 2-induced double cyclization of a beta-alkoxyacrylate and a double dihydroxylation for construction of the B- and E-rings.

  麦托毒素的BCDE环系统的立体选择性合成是通过双向策略构建多环醚而完成的。关键反应涉及SmI 2诱导的β-烷氧基丙烯酸酯的双环化和双二羟基化，以构建B环和E环。
• Stereoselective Synthesis of <i>trans</i>-Fused 7,6,6,7-Membered Tetracyclic Ether, Corresponding to the EFGH-Ring of Gambierol and the BCDE-Ring of Gambieric Acids
  作者：Tatsuo Saito、Tadashi Nakata

  DOI：10.1021/ol8024555

  日期：2009.1.1

  Stereoselective synthesis of a trans-fused 7,6,6,7-membered tetracyclic ether, corresponding to the EFGH-ring of gambierol and the BCDE-ring of gambieric acids, was efficiently accomplished via a two-directional approach. The key reactions were SMI2-induced double cyclization for construction of the F- and H-rings and SMI2-induced cyclization followed by ring expansion for construction of the E-ring.
• Solvent-Controlled Stereoselective Formation of a Cyclic Ether in the Lewis Acid-Mediated Allylation of an α-Chloroacetoxy Acyclic Ether. Very High Stereoselectivity in CH₃CN vs Low Stereoselectivity in CH₂Cl₂
  作者：Ilya D. Gridnev、Shigetoshi Kikuchi、Abeda S. Touchy、Isao Kadota、Yoshinori Yamamoto

  DOI：10.1021/jo7013752

  日期：2007.10.1

  The MgBr2-OEt2-mediated intramolecular allylation of a 4:1 diastereoisomeric mixture of the alpha-chloroacetoxyl ether la bearing the A-G/JK ring system of brevetoxin B in CH2Cl2 gave a 1: 1 diastereoisomeric mixture of the trans- and cis-cyclization products 4a and 5a having the A-G/I-K ring system, while that in CH3CN afforded the trans-isomer 4a nearly as the single product. To help clarify a reason for this marked solvent effect in the cyclization of the brevetoxin B precursor, DFT computations for the starting materials, intermediates, transition states, and products were carried out. The cyclization would proceed through a carbocation intermediate 3a having sp(2) flat structure (S(N)1 type mechanism) in CH2Cl2, in which the activation energies leading to both diastereoisomers are approximately identical, while in CH3CN alkylnitrilium salts 6a would be formed through the coordination of CH3CN to the carbocation leading to an sp(3)-type intermediate in which sever steric hindrance takes place in the transition state leading to the undesired diastereoisomer. The scope of this novel solvent-controlled stereo selectivity was tested for simple compounds. In small model compounds the marked solvent dependence was absent, but the model bearing two consecutive cyclic ether rings 1b exhibited a remarkable solvent effect similar to that observed in the brevetoxin B system.