(2S,6S)-2-tert-butyl-6-methyl-1,3-dioxan-4-one

• 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: (2S,6S)-2-tert-butyl-6-methyl-1,3-dioxan-4-one
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: SFWUTHYTQUXJTB-XPUUQOCRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,6S)-2-tert-butyl-6-methyl-1,3-dioxan-4-one 在 吡啶 、 4-二甲氨基吡啶 、 二氯二茂钛 、 三氟化硼乙醚 、 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 24.0h， 生成 [2(2SR,4RS,6SR)]-2-(2-tert-butyl-6-methyl-[1,3]dioxan-4-yl)-1-phenyl-ethanone
  参考文献：
  名称：

  1,3-Polyol arrays via the stereoselective rearrangement of vinyl acetals

  摘要：

  A series of 1,3-dioxanyl vinyl acetals were readily synthesized from the corresponding dioxanone by a reduction and in situ acylation followed by Petasis olefination. Treatment of these vinyl acetals with BF3 . OEt2 results in an O to 5 rearrangement to form anti-3,5-dihydroxyketones while a mixture of Me3Al and BF3.OEt2 provides the corresponding syn relationship via a stereoretentive rearrangement. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.03.004
• 作为产物：
  描述：

  特戊醛 、 DL-3-羟基丁酸 在 异丙氧基三甲基硅烷 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 以42%的产率得到(2S,6S)-2-tert-butyl-6-methyl-1,3-dioxan-4-one
  参考文献：
  名称：

  1,3-Polyol arrays via the stereoselective rearrangement of vinyl acetals

  摘要：

  A series of 1,3-dioxanyl vinyl acetals were readily synthesized from the corresponding dioxanone by a reduction and in situ acylation followed by Petasis olefination. Treatment of these vinyl acetals with BF3 . OEt2 results in an O to 5 rearrangement to form anti-3,5-dihydroxyketones while a mixture of Me3Al and BF3.OEt2 provides the corresponding syn relationship via a stereoretentive rearrangement. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.03.004

文献信息

• Absolute Configurations of Melanoxadin, MR-93A, Melanoxazal, and MR-93B
  作者：Tian-Jun He、Shijun Zhu、Xiao-Wei Lu、Yikang Wu、Yan Li

  DOI：10.1002/ejoc.201403287

  日期：2015.1

  Fungal metabolites melanoxadin, MR-93A, melanoxazal, and MR-93B were synthesized with the key stereogenic centers derived from commercially available chiral building blocks. The optically active synthetic products with well-defined absolute configurations provided authentic samples for the stereoisomers of these oxazole-containing natural products and thus allowed for unambiguous assignments of their

  真菌代谢物 melanoxadin、MR-93A、melanoxazal 和 MR-93B 是用衍生自市售手性构件的关键立体中心合成的。具有明确定义的绝对构型的旋光合成产品为这些含恶唑的天然产物的立体异构体提供了可靠的样品，因此可以明确分配它们的相对和绝对构型。讨论了天然和纯合成样品之间旋光度的巨大差异。之前报告的 NMR 信号分配中的一些错误也得到了纠正。
• Stereocontrolled synthesis of substituted tetrahydropyrans from 1,3-dioxan-4-ones
  作者：Nicos A. Petasis、Shao-Po Lu

  DOI：10.1016/0040-4039(95)02114-0

  日期：1996.1

  Conversion of aldehydes to 1,3-dioxan-4-ones, followed by methylenation with dimethyl titanocene gave the corresponding vinyl acetals which could undergo a stereocontrolled aluminum-mediated rearrangement to afford substituted tetrahydropyrans.

  将醛转化为1,3-二恶烷-4-酮，然后用二甲基二茂钛进行亚甲基化，得到相应的乙烯基缩醛，该缩醛可以进行立体控制的铝介导的重排，从而得到取代的四氢吡喃。
• Dendritic TADDOLs: Synthesis, Characterization and Use in the Catalytic Enantioselective Addition of Et2Zn to Benzaldehyde
  作者：P. Beat Rheiner、Dieter Seebach

  DOI：10.1002/(sici)1521-3765(19991105)5:11<3221::aid-chem3221>3.0.co;2-p

  日期：1999.11.5

  The versatile chiral ligand for polar metal centers, TADDOL ((R,R)alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-di-methanol), has been incorporated as core building block into dendrimers by way of benzylation of a fourfold phenolic derivative (hexol 2) with Frechet-type branches of up to fourth generation. These carry either benzyl (3-7) or octyl groups (33 -35) at the periphery, or they contain chiral branching units (18 - 20, 36), derived from (R)- or (S)-3-hydroxybutanoic acid. The dendritic compounds of molecular weight up to 13626 have been fully characterized, including by MALDI-TOF mass spectrometry, NMR spectroscopy, and optical activity measurements; one of the branch precursors with four octyl groups crystallized in an intriguing packing pattern. From the spectra and from the specific and molar optical rotations, there was no indication for the formation of chiral secondary structures of up to the third generation. The new TADDOLs were converted to Ti TADDOLates, which were employed as catalysts for the addition of Et2Zn to PhCHO. The stereoselectivities and the reaction rates observed with the novel catalysts were compared with those of the simple Ti TADDOLate: up to the second generation there was no detectable decrease of selectivity (= 98:2), and the rates hardly decreased up to the third generation; also, enantiomeric branches caused no change of stereoselectivity within experimental error. Thus, there may be applications for the special properties (such as high molecular weight, good solubility, spacing of central site from cross-linked polymer matrix) of dendritically modified chiral catalyst ligands.
• Use of Acid Fluorides Increases the Scope of the Reductive Acylation of Esters
  作者：Yongda Zhang、Tomislav Rovis

  DOI：10.1021/ol049333h

  日期：2004.5.1

  The use of acyl fluorides in the Rychnovsky reductive acylation of esters allows a variety of esters to be converted to their corresponding alpha-acyloxy ethers in good to excellent yields, without the need to sacrifice an extra equiv of carboxylic acid functionality.
• 1,3-Polyol arrays via the stereoselective rearrangement of vinyl acetals
  作者：Yongda Zhang、Tomislav Rovis

  DOI：10.1016/j.tet.2003.03.004

  日期：2003.11

  A series of 1,3-dioxanyl vinyl acetals were readily synthesized from the corresponding dioxanone by a reduction and in situ acylation followed by Petasis olefination. Treatment of these vinyl acetals with BF3 . OEt2 results in an O to 5 rearrangement to form anti-3,5-dihydroxyketones while a mixture of Me3Al and BF3.OEt2 provides the corresponding syn relationship via a stereoretentive rearrangement. (C) 2003 Elsevier Ltd. All rights reserved.