(+/-)-trans-(2-((tert-butyldimethylsilyloxy)methyl)cyclohexyl)methanol

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (+/-)-trans-(2-((tert-butyldimethylsilyloxy)methyl)cyclohexyl)methanol
• 英文别名: trans-2-(tert-butyldimethylsilyloxymethyl)cyclohexanemethanol；[(1R,2R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclohexyl]methanol
• 化学式: C₁₄H₃₀O₂Si
• 分子量: 258.476
• InChiKey: AIPGBEKUYFCANE-STQMWFEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.81
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-trans-(2-((tert-butyldimethylsilyloxy)methyl)cyclohexyl)methanol 在 咪唑 、 sodium hydride 、 三苯基膦 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 73.83h， 生成 (3aR,4R,7S,7aS)-2-(((1R,2R)-2-(((tert-butyldimethylsilyl)oxy)methyl)cyclohexyl)methyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione
  参考文献：
  名称：

  Efficient Syntheses of Diverse, Medicinally Relevant Targets Planned by Computer and Executed in the Laboratory

  摘要：

  The Chematica program was used to autonomously design synthetic pathways to eight structurally diverse targets, including seven commercially valuable bioactive substances and one natural product. All of these computer-planned routes were successfully executed in the laboratory and offer significant yield improvements and cost savings over previous approaches, provide alternatives to patented routes, or produce targets that were not synthesized previously.

  DOI：

  10.1016/j.chempr.2018.02.002
• 作为产物：
  描述：

  diethyl cyclohexane-trans-1,2-dicarboxylate 反应 24.0h， 生成 (+/-)-trans-(2-((tert-butyldimethylsilyloxy)methyl)cyclohexyl)methanol
  参考文献：
  名称：

  A C-B-A-D approach to brassinosteroids; Generation of the cis-anti-trans A-B-C ring system

  摘要：

  Thermal intramolecular Diels-Alder cyclisation of the ketone C-1 proceeds through an exo transition state to give the ketone CAT-2. (C) 1997 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00648-5

文献信息

• Dearomatization of Indole via Intramolecular [3 + 2] Cycloaddition: Access to the Pentacyclic Skeleton of<i>Strychons</i>Alkaloids
  作者：Zhengshen Wang、Luxin Chen、Yuan Yao、Zhigang Liu、Jin-Ming Gao、Xuegong She、Huaiji Zheng

  DOI：10.1021/acs.orglett.8b01720

  日期：2018.8.3

  polycyclic indoline-annulated normal to medium-size rings through dearomatization of indole via a tandem 1,2-acyloxy migration/intramolecular [3 + 2] cycloaddition process is described. The pentacyclic skeleton of strychnine could be synthesized via this tandem cycloaddition and a further Mannich reaction. This approach would provide a novel strategy to the synthesis of strychons alkaloids.

  描述了一种通过串联的1,2-酰氧基迁移/分子内[3 + 2]环加成过程使吲哚脱芳香化来构建各种多取代的多环吲哚啉环化的中型至中型环的有效方法。士的宁的五环骨架可以通过这种串联环加成反应和进一步的曼尼希反应合成。这种方法将提供一种新的策略来合成拟苯丙酸杆菌生物碱。
• Scope of Stereoselective Mn-Mediated Radical Addition to Chiral Hydrazones and Application in a Formal Synthesis of Quinine
  作者：Gregory K. Friestad、An Ji、Jonas Baltrusaitis、Chandra Sekhar Korapala、Jun Qin

  DOI：10.1021/jo2026349

  日期：2012.4.6

  favored an undesired azabicyclo[3.2.1]octane ring system, an outcome that was found to be consistent with transition state calculations at the B3LYP/6-31G(d) level. Group differentiation at an earlier stage enabled an alternative regioconvergent pathway; this furnished the desired azabicyclo[2.2.2]octane ring system and afforded quincorine (21b), completing a formal synthesis of quinine.

  立体控制的锰介导的烷基碘与手性N-酰基腙的加成能够在手性胺的立体中心构建战略性 C-C 键。将此策略应用于奎宁提出了互补的合成方法，使用多功能烷基碘6a - d作为自由基前体，或使用多功能手性N-酰基腙26a - d作为自由基受体，构建连接在含氮立体中心的 C-C 键。这些被包括在锰介导的各种烷基碘与一系列手性N 的自由基加成中-酰基腙自由基受体，导致发现吡啶和烯烃官能团不相容。在修改后的策略中，在 Mn 介导的自由基加成6d到手性N-酰基腙22b过程中避免了这些功能，它在奎宁的手性胺碳上产生了一个具有完全立体化学控制的关键 C-C 键。随后的阐述包括两个连续环化以完成氮杂双环 [2.2.2] 辛烷环系统。第二次环化期间两个 2-碘乙基之间的基团选择性有利于不希望的氮杂双环 [3.2.1] 辛烷环系统，发现这一结果与 B3LYP/6-31G(d) 水平的过渡态计算一致。早期的群体分化启用了
• Rhodium(I)-Catalyzed Hydroacylation/Cycloisomerization Cascade Reaction: Application to the Construction of the Tricyclic Core of Guanacastepenes
  作者：Yoshihiro Sato、Yoshihiro Oonishi、Ai Taniuchi

  DOI：10.1055/s-0030-1258184

  日期：2010.9

  developed a novel rhodium(I)-catalyzed cascade reaction involving the hydroacylation of a 4,6-dienal followed by cycloisomerization of the resulting 1,3-diene with an alkene, giving carbocycles containing a bicyclo[5.3.0]decenone skeleton in a stereoselective manner. Herein, we report the construction of the C5,C7,C6-tricyclic core of guanacastepenes using this cascade reaction. rhodium - cascade reactions

  我们先前开发了一种新型的铑（I）催化的级联反应，涉及4,6-二烯的加氢酰化，然后将生成的1,3-二烯与烯烃进行环异构化，从而得到含有双环[5.3.0]癸烯酮骨架的碳环以立体选择的方式。在本文中，我们报道了使用该级联反应构建胍卡斯汀的C 5，C 7，C 6-三环核。 铑-级联反应-二烯-醛-胍卡斯汀
• Absence of the alleged retardation of the Diels–Alder reaction for dienes bearing a neighbouring hydroxy substituent
  作者：Paul Glossop、David W. Jones

  DOI：10.1039/p19960000501

  日期：——

  ring-opening accompanies adduction to give 11 and two stereoisomers of gross structure 12. Dienes 1, 9 (X = OMe) and 9 (X = H) react at similar rates with N-methylmaleimide, discounting the alleged intramolecular retardation due to through space interaction between the hydroxy group and the diene system.

  与早先的观察相反，二烯1在Diels-Alder添加物中容易反应。用N-甲基马来酰亚胺等量地形成立体异构加合物10a和10b。在顺丁烯二酸酐的情况下，开环伴随加成得到11和两个总体结构12的立体异构体。二烯1，9（X = OMe）和9（X = H）与N-甲基马来酰亚胺的反应速率相似，从而消除了所谓的分子内阻滞作用。由于羟基和二烯系统之间通过空间相互作用。
• Quinine Synthesis Studies:  A Radical−Ionic Annulation via Mn-Mediated Addition to Chiral <i>N</i>-Acylhydrazones
  作者：Chandra Sekhar Korapala、Jun Qin、Gregory K. Friestad

  DOI：10.1021/ol7017938

  日期：2007.10.1

  A radical-ionic annulation approach to functionalized perhydroisoquinolines involving Mn-mediated coupling of alkyl iodides and chiral N-acylhydrazones was achieved using only 1.25 equiv of the alkyl iodide. Application of this reaction to alkene-containing substrates en route to quinine offered modest yields, decreasing on scaleup. Control experiments revealed that the alkene interfered with the coupling reaction. A revised approach involving prior oxidation of the alkene offered 93% yield in the Mn-mediated coupling, with the adduct obtained as a single diastereomer.