(R)-(2,3-dimethylcyclohex-1-enyloxy)trimethylsilane | 184422-45-5

• 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: (R)-(2,3-dimethylcyclohex-1-enyloxy)trimethylsilane
• 英文别名: [(3R)-2,3-dimethylcyclohexen-1-yl]oxy-trimethylsilane
• CAS: 184422-45-5
• 化学式: C₁₁H₂₂OSi
• 分子量: 198.381
• InChiKey: QPZWPRZVMYPSSL-SECBINFHSA-N

物化性质

• 沸点：
  197.1±8.0 °C(Predicted)
• 密度：
  0.87±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.93
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  丁烯酮 、 (R)-(2,3-dimethylcyclohex-1-enyloxy)trimethylsilane 在 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 硝基甲烷 为溶剂， 反应 6.0h， 生成 (-)-(4aS,5R)-4,4a,5,6,7,8-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone
  参考文献：
  名称：

  Total Syntheses of Anominine and Tubingensin A

  摘要：

  A divergent strategy for the total syntheses of the indole terpenoid anominine (1) and its natural congener tubingensin A (2) has been developed. The common intermediate 11 bearing all of the required stereogenic centers for both natural products was first assembled by employing a Ueno-Stork radical cyclization and a Sc(OTf)(3)-mediated Mukaiyama aldol reaction to form the key C-C bonds in a stereocontrolled manner. The route to anominine features a radical deoxygenation followed by an efficient side-chain installation, while the path to tubingensin A exploits a CuOTf-promoted 6 pi-electrocyclization/aromatization sequence to forge the central region of the pentacyclic scaffold.

  DOI：

  10.1021/ja302765m
• 作为产物：
  描述：

  三甲基氯硅烷 、 2,3-dimethylcyclohexanone 在 六甲基二硅氮烷 、 sodium iodide 作用下， 以 乙腈 为溶剂， 反应 2.0h， 生成 (R)-(2,3-dimethylcyclohex-1-enyloxy)trimethylsilane
  参考文献：
  名称：

  Total Syntheses of Anominine and Tubingensin A

  摘要：

  A divergent strategy for the total syntheses of the indole terpenoid anominine (1) and its natural congener tubingensin A (2) has been developed. The common intermediate 11 bearing all of the required stereogenic centers for both natural products was first assembled by employing a Ueno-Stork radical cyclization and a Sc(OTf)(3)-mediated Mukaiyama aldol reaction to form the key C-C bonds in a stereocontrolled manner. The route to anominine features a radical deoxygenation followed by an efficient side-chain installation, while the path to tubingensin A exploits a CuOTf-promoted 6 pi-electrocyclization/aromatization sequence to forge the central region of the pentacyclic scaffold.

  DOI：

  10.1021/ja302765m

文献信息

• Synthesis of Novel Functionalized Polymers for the Diastereoselective Protonation of Chiral Enolates
  作者：Marc Mackenstedt、Norbert Krause

  DOI：10.1002/ejoc.200400429

  日期：2004.11

  The polymeric, chelating proton donors 7 and 8 were synthesized by radical polymerization of the monomers 5/6 with different amounts of styrene. Protonation of chiral lithium enolates derived from silyl enol ethers 9 gave cis/trans ratios of up to 94:6 (10a) and 99:1 (10b), respectively. The polymers can be recycled and used repeatedly without appreciable loss of selectivity. (© Wiley-VCH Verlag GmbH

  聚合的螯合质子供体 7 和 8 是通过单体 5/6 与不同量苯乙烯的自由基聚合合成的。衍生自甲硅烷基烯醇醚 9 的手性烯醇锂的质子化分别产生高达 94:6 (10a) 和 99:1 (10b) 的顺/反比。聚合物可以回收和重复使用而不会明显降低选择性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• The first synthesis of ent-agelasine F
  作者：Ágnes Proszenyák、Morten Brændvang、Colin Charnock、Lise-Lotte Gundersen

  DOI：10.1016/j.tet.2008.10.081

  日期：2009.1

  Agelasine F has previously been isolated from marine sponges (Agelas sp.) and has been associated with various bioactivities including inhibitory activity on Mycobacterium tuberculosis. No total synthesis of this natural product has been reported. ent-Agelasine F has now been synthesized for the first time, starting from (R)-pulegone. The synthesis is considerably more efficient than a previously reported route to rac-agelasine F. ent-Agelasine F is found to exhibit antimicrobial activity. (C) 2008 Elsevier Ltd. All rights reserved.
• Synthesis of (+)-striatene: confirmation of its stereostructure
  作者：Paul Brémond、Nicolas Vanthuyne、Gérard Audran

  DOI：10.1016/j.tetlet.2009.07.138

  日期：2009.10

  The first enantioselective synthesis of natural striatene (+)-1, isolated from liverwort Ptychanthus striatus, starting from commercially available (R)-Pulegone is described. Its stereostructure was confirmed by X-ray analysis of a 3,5-dinitrobenzoate derivative obtained from a key intermediate and its high optical purity was verified by chiral HPLC. (C) 2009 Elsevier Ltd. All rights reserved.
• An efficient synthesis of the natural (+)-fulvanin 1
  作者：Philippe Dagneau、Perséphone Canonne

  DOI：10.1016/0957-4166(96)00370-9

  日期：1996.10

  Pulegone was used for the first total synthesis of (+)-fulvanin 1 adopting chiron approach. Pertinent methodology includes stereocontrolled Michael-type reaction, functional group adjustements and Wittig olefination. Copyright (C) 1996 Elsevier Science Ltd
• Total Syntheses of Anominine and Tubingensin A
  作者：Ming Bian、Zhen Wang、Xiaochun Xiong、Yu Sun、Carlo Matera、K. C. Nicolaou、Ang Li

  DOI：10.1021/ja302765m

  日期：2012.5.16

  A divergent strategy for the total syntheses of the indole terpenoid anominine (1) and its natural congener tubingensin A (2) has been developed. The common intermediate 11 bearing all of the required stereogenic centers for both natural products was first assembled by employing a Ueno-Stork radical cyclization and a Sc(OTf)(3)-mediated Mukaiyama aldol reaction to form the key C-C bonds in a stereocontrolled manner. The route to anominine features a radical deoxygenation followed by an efficient side-chain installation, while the path to tubingensin A exploits a CuOTf-promoted 6 pi-electrocyclization/aromatization sequence to forge the central region of the pentacyclic scaffold.