(+)-1R,5S-1,5-Dimethyl-6,8-dioxabicyclo[3.2.1]octane | 57917-96-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (+)-1R,5S-1,5-Dimethyl-6,8-dioxabicyclo[3.2.1]octane
• 英文别名: (1R,5S)-1,5-dimethyl-6,8-dioxabicyclo[3.2.1]octane；(+)-frontalin；(-)-Frontalin
• CAS: 57917-96-1
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: AZWKCIZRVUVZPX-SFYZADRCSA-N

物化性质

• 沸点：
  67-72 °C(Press: 30-35 Torr)
• 密度：
  1.056±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  5-氯-2-戊酮 生成 (+)-1R,5S-1,5-Dimethyl-6,8-dioxabicyclo[3.2.1]octane
  参考文献：
  名称：

  (-)-Frontalin：使用二甲基锌对酮的催化对映选择性加成合成

  摘要：

  (-)-frontalin 的第一次对映选择性合成，包括在四异丙醇钛和亚化学计量量的手性配体 1,2-反式存在下，二甲基锌与功能化 α,β-不饱和酮的对映选择性亲核 1,2-加成-双（羟基樟脑磺酰氨基）环己烷 (HOCSAC, 2) 作为关键步骤，进行了描述。对映体过量高达 89%。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejoc.200300261

文献信息

• A Catalytic Enantioselective Route to Hydroxy-Substituted Quaternary Carbon Centers:  Resolution of Tertiary Aldols with a Catalytic Antibody
  作者：Benjamin List、Doron Shabat、Guofu Zhong、James M. Turner、Anthony Li、Tommy Bui、James Anderson、Richard A. Lerner、Carlos F. Barbas

  DOI：10.1021/ja991507g

  日期：1999.8.1

  antibody catalyzed retro-aldol reactions. The catalytic proficiency, (kcat/KM)/kuncat, of the antibody for these reactions was on the order of 1010 M-1. A fluorogenic tertiary aldol allowed for the quantitative study of enantiomeric excess as a function of reaction conversion, revealing an E value of ca. 160 in this case. Study of a variety of substrates demonstrated that antibody-catalyzed retro-aldolization

  研究了醛缩酶抗体 38C2 催化的三级醛缩分解。三级羟醛被证明是用于抗体催化的逆羟醛反应的非常好的底物。抗体对这些反应的催化效率 (kcat/KM)/kuncat 约为 1010 M-1。荧光叔醛醇允许对映体过量作为反应转化的函数进行定量研究，揭示了约的 E 值。在这种情况下为 160。对各种底物的研究表明，抗体催化的逆醛醇化可快速进入高度对映异构体富集的叔醛醇，通常>95% ee，含有结构不同的杂原子取代的季碳中心。这种方法对天然产物合成的效用已通过 (+)-frontalin 的合成得到证明，
• A Chiral Benzyl Group as a Chiral Auxiliary and Protecting Group for the Synthesis of Optically Active 1,2-Diols and (+)-Frontalin
  作者：Hee-Doo Kim、Tae Kim、Young-Kyo Kim、Zunhua Yang、Jung Jung、Lak Jeong

  DOI：10.1055/s-0033-1340163

  日期：——

  Chelation-controlled asymmetric nucleophilic addition of a Grignard reagent to chiral α-benzyloxy ketones gives the corresponding alcohols with high diastereoselectivities (up to 96% de) by 1,4-asymmetric induction. A chiral benzyl group is used as a chiral auxiliary as well as a protecting group for the synthesis of optically active 1,2-diols and (+)-frontalin.

  格氏试剂与手性 α-苄氧基酮的螯合控制的不对称亲核加成通过 1,4-不对称诱导产生具有高非对映选择性（高达 96% de）的相应醇。手性苄基用作手性助剂和保护基团，用于合成光学活性 1,2-二醇和 (+)-frontalin。
• The absolute configuration of 6,8-dioxabicyclo[3.2.1]octane and several methyl substituted derivatives
  作者：N. Ibrahim、T. Eggimann、E.A. Dixon、H. Wieser

  DOI：10.1016/s0040-4020(01)81959-1

  日期：1990.1

  enantiomers of 6,8-dioxabicyclo[3.2.1]octane and the alkyl substituted derivatives, exo- and endo-7-methyl, exo- and endo-5,7-dimethyl, 7,7-dimethyl, and exo- and endo-7-ethyl-5-methyl (exo- and endo-brevicomin), were synthesized stereoselectively with known configuration by standard synthetic methods, or with baker's yeast, or both. The correlation between the absolute configuration of the bicyclic rings and

  6,8-二氧杂双环[3.2.1]辛烷的对映异构体和烷基取代的衍生物，exo-和内部-7-甲基，exo-和内部-5,7-二甲基，7,7-二甲基和exo-和内-7-乙基-5-甲基（外-和内-brevicomin），通过已知的构型，通过标准合成方法，或与面包酵母，或两者，立体选择性地合成。通过手性络合气相色谱法建立了两个分子的双环绝对构型与旋光性之间的相关性，此前尚不知道这种相关性。在所有情况下，（1R）对映异构体均显示正旋转。建立了始终以高光学纯度生产的酵母产品的绝对构型。
• Preparation of Substituted Enol Derivatives From Terminal Alkynes and Their Synthetic Utility
  作者：John R. DeBergh、Kathleen M. Spivey、Joseph M. Ready

  DOI：10.1021/ja803480b

  日期：2008.6.1

  trapping with carboxylic anydrides or silyl triflates yields trisubstituted enol esters or silanes, respectively. The tandem carbometalation/oxygenation tolerates free and protected alcohols, heterocycles, olefins, and nitriles. Stereodefined enol esters can undergo asymmetric dihydroxylation to yield optically active alpha-hydroxy aldehydes. Reduction with NaBH4 provides the diols of 1,1-disubstituted olefins

  醛的立体定义的烯醇衍生物由末端炔烃制备。具体而言，已知末端炔烃会经历 Cp2ZrCl2 催化的甲基铝化。在这里，我们表明所得的乙烯丙烷可以用过氧锌物质氧化以生成三取代的烯醇化物。用羧酸酐或甲硅烷基三氟甲磺酸酯进行亲电捕获分别产生三取代的烯醇酯或硅烷。串联碳金属化/氧化耐受游离和受保护的醇、杂环、烯烃和腈。立体定义的烯醇酯可以进行不对称二羟基化以产生光学活性的 α-羟基醛。用 NaBH4 还原以优异的 ee 提供 1,1-二取代烯烃的二醇。介绍了这种方法在昆虫信息素额蛋白的对映选择性合成中的应用。最后，显示 α-羟基醛经过同系化到末端炔、还原胺化、氧化和烯化。初步结果表明串联碳金属化/胺化可以用偶氮二羧酸盐完成。以这种方式，以极好的收率形成烯-肼。
• Chiral linker. Part 4: Diastereoselective addition of RZnX to α-keto esters using m-hydrobenzoin derived chiral auxiliaries in solution and on solid support and their application in the stereoselective synthesis of frontalin
  作者：Christian Schuster、Max Knollmueller、Peter Gaertner

  DOI：10.1016/j.tetasy.2006.08.016

  日期：2006.9

  Two recently reported, m-hydrobenzoin derived open chain chiral auxiliaries, which were developed for application in either solution or immobilized on a solid support, were tested in the diastereoselective addition of RZnX to their corresponding phenylglyoxylates and pyruvates, respectively, resulting in diastereoisomeric excesses of up to > 98% de. The optimized procedure was applied in the stereoselective synthesis of frontalin, the aggregation pheromone of pine bark beetles of the Dendroctonus family, by the use of both the solution phase and the polymer supported chiral auxiliary. (c) 2006 Elsevier Ltd. All rights reserved.