cis-5,6-dihydro-6-(hydroxymethyl)-2-methoxy-2H-pyran | 321994-96-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: cis-5,6-dihydro-6-(hydroxymethyl)-2-methoxy-2H-pyran
• 英文别名: [(2R,6S)-6-methoxy-3,6-dihydro-2H-pyran-2-yl]methanol
• CAS: 321994-96-1
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: USWZSVOYTUOFIM-RQJHMYQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cis-5,6-dihydro-6-(hydroxymethyl)-2-methoxy-2H-pyran 在 palladium diacetate potassium tert-butylate 、 四丁基溴化铵 、 4-甲基苯磺酸吡啶 、 caesium carbonate 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 、 丙酮 、 甲苯 为溶剂， 生成 (R)-6-{(1E,3Z,7E,9E)-(5R,11R)-11-(tert-Butyl-dimethyl-silanyloxy)-11-[(2S,4R,5R,6S)-4-(tert-butyl-dimethyl-silanyloxy)-5-methyl-6-((E)-propenyl)-tetrahydro-pyran-2-yl]-3,5,7-trimethyl-undeca-1,3,7,9-tetraenyl}-5,6-dihydro-2H-pyran-2-ol
  参考文献：
  名称：

  Total Synthesis of (+)-Ratjadone

  摘要：

  DOI：

  10.1002/1521-3773(20001201)39:23<4364::aid-anie4364>3.0.co;2-g
• 作为产物：
  描述：

  ethyl 2-methoxy-5,6-dihydro-2H-pyran-6-carboxylate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 cis-5,6-dihydro-6-(hydroxymethyl)-2-methoxy-2H-pyran
  参考文献：
  名称：

  Synthesis of unsaturated lactone moieties by asymmetric hetero Diels–Alder reactions with binaphthol-titanium complexes

  摘要：

  Natural products like ratjadone and callystatin A contain an alpha,beta -unsaturated lactone moiety which adds to the biological activity of these compounds. Here we report a rapid and practical access to lactone precursor 3 by an asymmetric hetero Diels-Alder reaction as the key step and its subsequent transformation into a suitable building block 4. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)02213-9

文献信息

• Asymmetric Catalysis of Diels-Alder Cycloadditions by an MS-Free Binaphthol-Titanium Complex: Dramatic Effect of MS, Linear vs Positive Nonlinear Relationship, and Synthetic Applications
  作者：Koichi Mikami、Yukihiro Motoyama、Masahiro Terada

  DOI：10.1021/ja00086a014

  日期：1994.4

  Asymmetric Diels-Alder (D.-A.) reaction of 5-hydroxynaphthoquinone (juglone) with butadienyl acetate catalyzed by the binaphthol-derived chiral titanium (BINOL-Ti) complex 1 proceeds in only 9% ee in the presence of molecular sieves (MS). Remarkably, however, this reaction proceeds in 76-96% ee with BINOL-Ti complex 1 freed from MS to provide the endo-adducts useful for the synthesis of anthracyclines and tetracyclines. The solid MS-free BINOL-Ti complex 1 is stable for months at -20 degrees C, Enhancements in endo selectivity and asymmetric induction are observed with the MS-free BINOL-Ti 1 also in the catalyzed D.-A. cycloaddition of methacrolein and glyoxylate with 1,3-dienol ethers and esters. The glyoxylate adducts can be converted to the mevinolin (compactin) intermediates. Surprisingly, the MS-free complex 1 exhibits not only a linear relationship between the ee's of BINOL-Ti 1 and the D.-A. products but also a positive nonlinear effect (asymmetric amplification), depending simply on the mixing manner of (R)-1 with (S)-1 or (+/-)-1.
• The First Total Synthesis of (+)-Ratjadone
  作者：Ulhas Bhatt、Mathias Christmann、Monika Quitschalle、Eckhard Claus、Markus Kalesse

  DOI：10.1021/jo005768g

  日期：2001.3.1

  The first total synthesis of ratjadone was achieved using a highly convergent approach joining three subunits together with a Wittig olefination and a selective Heck reaction as the pivotal steps. Besides establishing a robust and reliable route for the synthesis of this orphan ligand, the configuration of unknown stereocenters could also be determined. This synthesis not only provides an additional access to a biologically important compound but also enables the synthesis of structural analogues for biological target identification.