meso-1,4-difuran-2'-ylbutane-1,4-diol | 402491-10-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: meso-1,4-difuran-2'-ylbutane-1,4-diol
• 英文别名: (RS,SR)-1,4-difuran-2-ylbutane-1,4-diol；(1S,4R)-1,4-bis(furan-2-yl)butane-1,4-diol
• CAS: 402491-10-5
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: KHKYFTHMAVHOBZ-AOOOYVTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  66.7
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  meso-1,4-difuran-2'-ylbutane-1,4-diol 在 bis(acetylacetonate)oxovanadium 叔丁基过氧化氢 、 sodium tetrahydroborate 、 cerium(III) chloride 、 三氟化硼 、 三乙胺 作用下， 生成 methanesulfonic acid (2R,3S,6S)-2-{2-[(2S,3R,6R)-6-methoxy-3-methylsulfonyloxy-3,6-dihydro-2H-pyran-2-yl]ethyl}-6-methoxy-3,6-dihydro-2H-pyran-3-yl ester
  参考文献：
  名称：

  Directed and undirected asymmetric dihydroxylation reactions: application in the synthesis of a C-linked analogue of allolactose

  摘要：

  复合物 OsO4-(S,S)-1,2-二苯基-N,N′-双(2,4,6-三甲基苄基)乙烷-1,2-二胺是一种有效的试剂，可通过不对称二羟基化作用使中-1,2-双(3,6-二氢-2H-吡喃-2-基)乙烷非对称化；这一过程的非对映选择性取决于取代和立体化学，已被用于合成异半乳糖的 C 链类似物。

  DOI：

  10.1039/b107643d
• 作为产物：
  描述：

  1,4-di(2-furanyl)-1,4-butanedione 在 硼烷四氢呋喃络合物 、 (S)-2-甲基-CBS-恶唑硼烷 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 2.0h， 以80%的产率得到(1R,4R)-1,4-difuran-2'-ylbutane-1,4-diol
  参考文献：
  名称：

  立体异构C联二糖模拟物的立体发散的双向合成。

  摘要：

  以双吡喃酮类化合物为模板，合成了1,2-双[（2R，3S，6S）-3-羟基-6-甲氧基-3-氧代-6H-吡喃-2-基]乙烷C-联二糖类似物。开发了有效的方法，例如立体选择性还原和二羟基化，用于这些模板的双向功能化。十种立体异构二糖类似物[乙酸4,5-二乙酰氧基-6-甲氧基-[（3'，4'，5'-三乙酰氧基-6'-甲氧基四氢吡喃-2'-基）乙基]四氢吡喃-3-基的全乙酰化衍生物酯]是从136种化合物的虚拟文库中合成的；此外，通过在对映选择性步骤中使用对映体配体可以简单地合成另外八种立体异构体。（2S，3S，4R，5R，6R）-6-甲氧基-2- [2'-（（（2'R，3'R，4'S，5'R，6'S）-3'，4'，据估计，与阻遏蛋白LacI结合的5'-三羟基-6'-甲氧基四氢吡喃-2'-基）乙基]四氢吡喃-3,4,5-三醇与异丙基-β-硫代半乳糖苷相似。二糖模拟物被认为是一类新的有趣的C联二糖模

  DOI：

  10.1039/b208781b

文献信息

• Sequential kinetic resolution of C2-symmetric compounds as a key step in two-directional synthesis: structural requirements for efficient resolution of difuryl diols
  作者：Michael Harding、Robert Hodgson、Adam Nelson

  DOI：10.1039/b206478b

  日期：2002.10.29

  The C2-symmetrical diols (R*,R*)-1,4-difuran-2-yl-butane-1,4-diol 13 and (1R*,3S*,4S*,6R*)-3,4-bis(tert-butyldimethylsilyloxy)-1,6-difuran-2-yl-hexane-1,6-diol 26 were synthesised in a two-directional manner: the reductions of (3R*,4R*)-3,4-bis(tert-butyldimethylsilyloxy)-1,6-difuran-2-ylhexane-1,6-dione with DIBAL-H and Red-Al were remarkably 1,3syn selective, presumably as a result of reduction of chelates formed from the 3-silyloxy-1-(2-furyl)ketones. Sequential Sharpless kinetic resolutions of 13 and 26 were studied. The first step of the kinetic resolution of 26 was shown to proceed with an enantioselectivity factor of E = 1.9, and sequential resolution yielded the doubly oxidised product in 43% yield and 43% ee; this compares favourably with the enantiomeric excess (24% ee at 43% completion) of a product derived from a similarly enantioselective conventional kinetic resolution. The structural features of C2-symmetric substrates which are required for efficient sequential kinetic resolution, and the relevance of these reactions in two-directional syntheses, are discussed.

  (R*,R*)-1,4-二呋喃-2-基-丁烷-1,4-二醇 13 和 (1R*,3S*,4S*,6R*)-3,4-双(叔丁基二甲基硅氧基)-1,6-二呋喃-2-基-己烷-1,6-二醇 26 的 C2 对称二醇以双向方式合成：用 DIBAL-H 和 Red-Al 还原 (3R*,4R*)-3,4-双(叔丁基二甲基硅氧基)-1,6-二呋喃-2-基己烷-1,6-二酮时，1,3syn 具有显著的选择性，这可能是由于 3-硅氧基-1-(2-呋喃基)酮形成的螯合物被还原的结果。研究了 13 和 26 的 Sharpless 顺序动力学解析。结果表明，26 的第一步动力学解析的对映选择性系数为 E = 1.9，顺序解析产生的双氧化产物的收率为 43%，ee 为 43%；这与类似对映选择性的传统动力学解析产生的产物的对映过量（完成度为 43% 时的ee 为 24%）相比更为有利。本文讨论了高效顺序动力学解析所需的 C2 对称底物的结构特征，以及这些反应在双向合成中的相关性。
• Desymmetrisation of meso difuryl alcohols, diols and their derivatives: complementary directed and undirected asymmetric dihydroxylation reactions
  作者：Robert Hodgson、Tahir Majid、Adam Nelson

  DOI：10.1039/b204904j

  日期：2002.7.11

  Asymmetric reactions (for example, asymmetric epoxidation and asymmetric dihydroxylation) were examined for the desymmetrisation of the meso substrates 1,1-difuran-2-ylmethanol, N-(1,1-difuran-2-ylmethyl)-4-methylbenzenesulfonamide, (R,S)-1,4-difuran-2-ylbutane-1,4-diol and the derivatives of these compounds. The complex OsO4·(S,S)-1,2-diphenyl-N,N′-bis(2,4,6-trimethylbenzyl)ethane-1,2-diamine was found to be an effective reagent for the desymmetrisation of meso-1,2-bis(3,6-dihydro-3-hydroxy-2H-pyran-2-yl)ethanes and the corresponding di-p-methoxybenzoates by asymmetric dihydroxylation. The stereochemical outcome of this process depends critically on the relative stereochemistry and substitution of the substrate, and can occur anti to, or be directed by, an allylic alcohol or p-methoxybenzoyloxy functional group.

  研究了 1,1-二呋喃-2-基甲醇、N-(1,1-二呋喃-2-基甲基)-4-甲基苯磺酰胺、(R,S)-1,4-二呋喃-2-基丁烷-1,4-二醇和这些化合物的衍生物的不对称反应（例如不对称环氧化反应和不对称二羟基化反应）。研究发现，OsO4-(S,S)-1,2-二苯基-N,N′-双(2,4,6-三甲基苄基)乙烷-1,2-二胺复合物是一种有效的试剂，可通过不对称二羟基化作用，使介-1,2-双(3,6-二氢-3-羟基-2H-吡喃-2-基)乙烷和相应的二对甲氧基苯甲酸酯发生去对称化反应。这一过程的立体化学结果主要取决于底物的相对立体化学性质和取代情况，并可能与烯丙基醇或对甲氧基苯甲酰氧基官能团发生反应或受其引导。
• Exploiting predisposition in the stereoselective synthesis of mono-, bi- and tetracyclic oxygen heterocycles: Equilibration between, and trapping of, alternative di- and tetraacetals
  作者：Stephen Bartlett、Robert Hodgson、Joanne M. Holland、Matthew Jones、Colin Kilner、Adam Nelson、Stuart Warriner

  DOI：10.1039/b303089j

  日期：——

  The desymmetrisation of 1,4-difuran-2-ylbutane-1,4-diol by Sharpless asymmetric oxidation gave the corresponding desymmetrised product in > 96% ee. However, the product existed as a mixture of two interconverting isomers, both of which were mixtures of anomers. The product could be trapped in high yield with a range of reagents to give stable adducts with embedded pyran-3-one, 1,6-dioxaspiro[4.5]decane or pyrano[3,2-b]pyran ring systems. The strategy was also applied in the interconversion between alternative tetracycles and, under acidic conditions, this process was thermodynamically controlled. The selectivity of the process was rationalised by molecular modelling using the HF/6-31G* parameter set.

  通过 Sharpless 不对称氧化法对 1,4-二呋喃-2-基丁烷-1,4-二醇进行去对称化反应，得到了相应的去对称化产物，ee > 96%。不过，该产物是两种相互转化的异构体的混合物，这两种异构体都是同分异构体的混合物。利用一系列试剂可以高产率地捕获该产物，从而得到嵌入吡喃-3-酮、1,6-二氧杂螺[4.5]癸烷或吡喃并[3,2-b]吡喃环系统的稳定加合物。该策略还应用于替代四环之间的相互转化，在酸性条件下，该过程受热力学控制。通过使用 HF/6-31G* 参数集进行分子建模，该过程的选择性得到了合理的解释。
• Directed and undirected asymmetric dihydroxylation reactions: application in the synthesis of a C-linked analogue of allolactose
  作者：Robert Hodgson、Tajir Mahid、Adam Nelson

  DOI：10.1039/b107643d

  日期：2001.10.11

  The complex OsO4·(S,S)-1,2-diphenyl-N, N′-bis(2,4,6-trimethylbenzyl)ethane-1,2-diamine is an effective reagent for the desymmetrisation of meso-1,2-bis(3,6-dihydro-2H-pyran-2-yl)ethanes by asymmetric dihydroxylation; this process, whose sense of diastereoselectivity depends on substitution and stereochemistry, has been exploited in the synthesis of a C-linked analogue of allolactose.

  复合物 OsO4-(S,S)-1,2-二苯基-N,N′-双(2,4,6-三甲基苄基)乙烷-1,2-二胺是一种有效的试剂，可通过不对称二羟基化作用使中-1,2-双(3,6-二氢-2H-吡喃-2-基)乙烷非对称化；这一过程的非对映选择性取决于取代和立体化学，已被用于合成异半乳糖的 C 链类似物。
• A stereodivergent, two-directional synthesis of stereoisomeric C-linked disaccharide mimetics
  作者：Michael Harding、Robert Hodgson、Tahir Majid、Kenneth J. McDowall、Adam Nelson

  DOI：10.1039/b208781b

  日期：2003.1.13

  as templates for the synthesis of some novel C-linked disaccharide analogues. Efficient methods, such as stereoselective reduction and dihydroxylation, were developed for two-directional functionalisation of these templates. Peracetylated derivatives of ten stereoisomeric disaccharide analogues [acetic acid 4,5-diacetoxy-6-methoxy-[(3',4',5'-triacetoxy-6'-methoxytetrahydropyran- 2'-yl)ethyl]tetrahydropyran-3-yl

  以双吡喃酮类化合物为模板，合成了1,2-双[（2R，3S，6S）-3-羟基-6-甲氧基-3-氧代-6H-吡喃-2-基]乙烷C-联二糖类似物。开发了有效的方法，例如立体选择性还原和二羟基化，用于这些模板的双向功能化。十种立体异构二糖类似物[乙酸4,5-二乙酰氧基-6-甲氧基-[（3'，4'，5'-三乙酰氧基-6'-甲氧基四氢吡喃-2'-基）乙基]四氢吡喃-3-基的全乙酰化衍生物酯]是从136种化合物的虚拟文库中合成的；此外，通过在对映选择性步骤中使用对映体配体可以简单地合成另外八种立体异构体。（2S，3S，4R，5R，6R）-6-甲氧基-2- [2'-（（（2'R，3'R，4'S，5'R，6'S）-3'，4'，据估计，与阻遏蛋白LacI结合的5'-三羟基-6'-甲氧基四氢吡喃-2'-基）乙基]四氢吡喃-3,4,5-三醇与异丙基-β-硫代半乳糖苷相似。二糖模拟物被认为是一类新的有趣的C联二糖模