(3R,5R)-(5-isopropenyl-2,3-dimethylcyclohex-1-enyloxy)trimethylsilane | 213833-70-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (3R,5R)-(5-isopropenyl-2,3-dimethylcyclohex-1-enyloxy)trimethylsilane
• 英文别名: [(3R,5R)-2,3-dimethyl-5-prop-1-en-2-ylcyclohexen-1-yl]oxy-trimethylsilane
• CAS: 213833-70-6
• 化学式: C₁₄H₂₆OSi
• 分子量: 238.445
• InChiKey: XFVNMJFXIQKUGV-DGCLKSJQSA-N

物化性质

• 沸点：
  260.5±40.0 °C(predicted)
• 密度：
  0.87±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.73
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  (3R,5R)-(5-isopropenyl-2,3-dimethylcyclohex-1-enyloxy)trimethylsilane 在 palladium on activated charcoal trityl perchlorate 、 氢气 、 叔丁基锂 、 臭氧 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 正戊烷 为溶剂， 反应 108.0h， 生成 (3S,4S,5R,2'S,3a'R,6a'S)-3-[3-([1,3]dioxolan-2-yl)propyl]-4-(hexahydrofuro[2,3-b]furan-2'-yl)-4,5-dimethylcyclohexanone
  参考文献：
  名称：

  Total Synthesis of Dihydroclerodin from (R)-(−)-Carvone

  摘要：

  The first total synthesis of the natural enantiomer of the insect-antifeedant dihydroclerodin (1) and lupulin C (40) has been achieved starting from (R)-(-)-carvone (2). In the applied strategy, the hexahydrofuro[2,3-b]furan moiety was introduced in an early stage of the synthesis. The correct configuration at C-9, C-11, C-13, and C-16 was established by application of a remarkably diastereoselective Mukaiyama reaction. The desired configuration at C-10 was obtained by catalytic reduction of the intermediate enone 21. After annulation of the second ring, the structural features at C-4, C-5, and C-6 were introduced. The successful finishing of the synthesis included a Chugaev elimination to give the exocyclic double bond at C-4 that is present in lupulin C. Oxidation of this double bond with m-CPBA afforded dihydroclerodin.

  DOI：

  10.1021/jo991151r
• 作为产物：
  描述：

  三甲基氯硅烷 、 (1R,4R,6S)-4-isopropenyl-1-methyl-bicyclo[4.1.0]heptan-2-one 在 2,3,5-三甲基吡啶 、 汞 、 锌 作用下， 以 四氢呋喃 为溶剂， 反应 13.0h， 以39%的产率得到(3R,5R)-(5-isopropenyl-2,3-dimethylcyclohex-1-enyloxy)trimethylsilane
  参考文献：
  名称：

  双环[4.1.0]酮的一些新型电子转移介导的级联开环反应

  摘要：

  描述了由碘化sa（II）和其他电子转移剂介导的环丙基酮的自由基开环反应。该策略允许串联重排环化反应以及通过各种亲电试剂捕获所得resultant（III）烯醇化物，以构建复杂的双环系统。

  DOI：

  10.1016/0040-4020(96)00635-7

文献信息

• The Kharasch reaction revisited: CuX3Li2-catalyzed conjugate addition reactions of Grignard reagents
  作者：Manfred T. Reetz、Alois Kindler

  DOI：10.1016/0022-328x(95)05699-p

  日期：1995.10

  The conjugate addition of Grignard reagents RMgX to α,β-unsaturated ketones and esters is effectively catalyzed by soluble copper ate-complexes of the type CuX3Li2, e.g. CuI · 2LiCl. In the presence of Me3SiCl the corresponding ketone enolsilanes are formed in high yield and selectivity. Diasteroselectivity in the case of chiral ketones is similar to that observed by using stoichiometric amounts of

  格氏试剂RMgX向α，β-不饱和酮和酯的共轭加成可通过CuX 3 Li 2类型的可溶性铜酸酯络合物（例如CuI·2LiCl ）有效地催化。在Me 3 SiCl存在下，可以高产率和高选择性形成相应的酮烯醇硅烷。在手性酮的情况下，非对映选择性类似于通过使用化学计量的铜酸盐R 2 CuLi所观察到的非对映选择性。因此，CuX 3 Li 2催化的格氏试剂的1，4-加成可能是工业上可行的方法。
• 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)
• Samarium(II) iodide promoted radical ring opening reactions of cyclopropyl ketones
  作者：Robert A. Batey、William B. Motherwell

  DOI：10.1016/0040-4039(91)80245-2

  日期：1991.11

  Radical ring opening reactions of cyclopropyl ketones mediated by samarium(II) iodide-induced single electron transfer have permitted the elaboration of a tandem rearrangement cyclisation strategy. The resultant samarium enolates may be effectively quenched on oxygen or carbon by electrophiles.

  由碘化sa（II）介导的单电子转移介导的环丙基酮的自由基开环反应已允许阐述串联重排环化策略。所得的烯醇化sa可以通过亲电试剂在氧或碳上有效地淬灭。
• Enantioselective synthesis of highly functionalised cyclohexanones starting from R-(−)-carvone
  作者：Tommi M. Meulemans、Gerrit A. Stork、Ben J.M. Jansen、Aede de Groot

  DOI：10.1016/s0040-4039(98)01367-7

  日期：1998.9

  Copper (I) catalysed conjugate addition of methylmagnesium iodide to R-(−)-carvone and trapping the enolate as its trimethylsilyl enol ether, followed by a trityl perchlorate (TrClO4) catalysed Mukaiyama-aldol reaction, is an efficient method for the preparation of highly functionalised cyclohexanones which can be used as starting compounds in the total syntheses of enantiomerically pure clerodanes

  铜（I）催化的碘化甲基镁共轭加成到R-（-）-香芹酮中，并捕获烯醇化物作为其三甲基甲硅烷基烯醇醚，然后高氯酸三苯酯（TrClO 4）催化Mukaiyama- aldol反应，是制备的一种有效方法高度官能化的环己酮的衍生物，可以用作对映体纯净的立达酮的全部合成中的起始化合物。
• Some novel electron transfer mediated cascade ring-opening reactions of bicyclo[4.1.0]ketones
  作者：Robert A. Batey、John D. Harling、William B. Motherwell

  DOI：10.1016/0040-4020(96)00635-7

  日期：1996.8

  The radical ring-opening reactions of cyclopropyl ketones, mediated by samarium (II) iodide and other electron transfer agents are described. This strategy allows tandem rearrangement cyclisation reactions and the trapping of the resultant samarium (III) enolates by a variety of electrophiles, for the construction of complex bicyclic systems.

  描述了由碘化sa（II）和其他电子转移剂介导的环丙基酮的自由基开环反应。该策略允许串联重排环化反应以及通过各种亲电试剂捕获所得resultant（III）烯醇化物，以构建复杂的双环系统。