(+)-4-<(Benzyloxy)methyl>-3-methyl-2-cyclohexen-1-one | 160062-62-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-4-<(Benzyloxy)methyl>-3-methyl-2-cyclohexen-1-one
• 英文别名: 4-((benzyloxy)methyl)-3-methylcyclohex-2-en-1-one；(4R)-3-methyl-4-(phenylmethoxymethyl)cyclohex-2-en-1-one
• CAS: 160062-62-4
• 化学式: C₁₅H₁₈O₂
• 分子量: 230.307
• InChiKey: RTARLOVOQHNUAD-AWEZNQCLSA-N

物化性质

• 沸点：
  350.212±21.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.052±0.06 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-4-<(Benzyloxy)methyl>-3-methyl-2-cyclohexen-1-one 在 copper(l) iodide 吡啶 、 4-二甲氨基吡啶 、 四甲基乙二胺 、 甲基锂 、 magnesium bromide 作用下， 反应 1.92h， 生成
  参考文献：
  名称：

  Tremorgenic Indole Alkaloids. 9. Asymmetric construction of an Advanced F-G-H-ring Lactone precursor for the Synthesis of Penitrem D

  摘要：

  Lactone (+)-12 is envisioned as the precursor to the F-G-H rings of penitrem D (4) in our ongoing synthetic venture. The efficient, stereocontrolled introduction of the vicinal quaternary methyl groups present the major challenge in the construction of this subunit. Our first route to (+/-)-12 was marked by low overall yield (<2%) and the instability of several key intermediates; these deficiencies were rectified in a second-generation approach that produced optically active material (18 steps from 19a, 2.1% overall). The successful strategies exploited enolate generation via either conjugate additions to alpha,beta-enones or the Evans oxy-Cope rearrangement as key regiochemical control elements.

  DOI：

  10.1021/jo00129a025
• 作为产物：
  描述：

  3-甲氧基-2-环己烯-1-酮 在 copper(l) iodide 氧气 、 rose bengal 、 二异丁基氢化铝 、 三苯基膦 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 12.5h， 生成 (+)-4-<(Benzyloxy)methyl>-3-methyl-2-cyclohexen-1-one
  参考文献：
  名称：

  Tremorgenic Indole Alkaloids. 9. Asymmetric construction of an Advanced F-G-H-ring Lactone precursor for the Synthesis of Penitrem D

  摘要：

  Lactone (+)-12 is envisioned as the precursor to the F-G-H rings of penitrem D (4) in our ongoing synthetic venture. The efficient, stereocontrolled introduction of the vicinal quaternary methyl groups present the major challenge in the construction of this subunit. Our first route to (+/-)-12 was marked by low overall yield (<2%) and the instability of several key intermediates; these deficiencies were rectified in a second-generation approach that produced optically active material (18 steps from 19a, 2.1% overall). The successful strategies exploited enolate generation via either conjugate additions to alpha,beta-enones or the Evans oxy-Cope rearrangement as key regiochemical control elements.

  DOI：

  10.1021/jo00129a025

文献信息

• BIMP‐Catalyzed 1,3‐Prototropic Shift for the Highly Enantioselective Synthesis of Conjugated Cyclohexenones
  作者：Jonathan C. Golec、Eve M. Carter、John W. Ward、William G. Whittingham、Luis Simón、Robert S. Paton、Darren J. Dixon

  DOI：10.1002/anie.202006202

  日期：2020.9.28

  A bifunctional iminophosphorane (BIMP)‐catalysed enantioselective synthesis of α,β‐unsaturated cyclohexenones through a facially selective 1,3‐prototropic shift of β,γ‐unsaturated prochiral isomers, under mild reaction conditions and in short reaction times, on a range of structurally diverse substrates, is reported. α,β‐Unsaturated cyclohexenone products primed for downstream derivatisation were obtained

  双功能亚氨基正膦 (BIMP) 催化对映选择性合成 α,β-不饱和环己烯酮，通过 β,γ-不饱和前手性异构体的表面选择性 1,3-质子转移，在温和的反应条件和短的反应时间内，在一系列据报道，结构多样的底物。用于下游衍生化的 α,β-不饱和环己烯酮产品以高收率（高达 99%）和一致的高对映选择性（高达 99% ee ）获得。对反应机理和对映选择性起源（包括 TS 能量的多元线性回归）进行了计算研究，发现所得数据与实验结果非常吻合。
• Enantioselective synthesis of the hexahydronaphthalene nucleus of (−)-compactin from ethyl (1R,2S)-2-methyl-4-oxocyclohexanecarboxylate and 2-(3-nitropropyl)-1,3-dioxolane as four carbon bifunctional annelating agent.
  作者：Achille Barco、Simonetta Benetti、Anna Bianchi、Alberto Casolari、Gian P Pollini、Romeo Romagnoli、Giampiero Spalluto、Vinicio Zanirato

  DOI：10.1016/s0040-4020(01)85667-2

  日期：1994.1

  An enantioselective approach to the synthesis of the hexahydronaphthalene nucleus of natural compactin is described. The key elements of the synthesis are as follows: (i) the preparation of the chiral starting material through enzymatic resolution of the readily available cis 2-methyl-4-oxocyclohexane carboxylic acid, (ii) conversion into the suitably protected (4S,5S)4-hydroxymethyl-5-methyl-2-cyclohexen-2-one

  描述了合成天然紧致蛋白的六氢萘核的对映选择性方法。合成的关键要素如下：（i）通过酶解易得的顺式制备手性原料2-甲基-4-氧代环己烷羧酸，（ii）通过区域选择性引入α，β-碳-碳转化为适当保护的（4S，5S）4-羟甲基-5-甲基-2-环己烯-2-酮Pd（II）催化的脱氢硅烷化作用形成双键，（iii）使用2-（3-硝基丙基）-1,3-二氧戊环作为四碳双官能化成环剂，将新的六元环构建到预先存在的碳骨架中（iv ）通过官能团处理将衍生的六氢萘酮加工成已经带到天然目标物的高级前体，包括在C-1处将硝基转化为氧化官能团，以及将烯丙醇脱水为所需的1,3-二烯部分。
• Tremorgenic Indole Alkaloids. 9. Asymmetric construction of an Advanced F-G-H-ring Lactone precursor for the Synthesis of Penitrem D
  作者：Amos B. Smith、Ernest G. Nolen、Ryuichi Shirai、Frances R. Blase、Mitsuaki Ohta、Noritaka Chida、Richard A. Hartz、Duke M. Fitch、William M. Clark、Paul A. Sprengeler

  DOI：10.1021/jo00129a025

  日期：1995.12

  Lactone (+)-12 is envisioned as the precursor to the F-G-H rings of penitrem D (4) in our ongoing synthetic venture. The efficient, stereocontrolled introduction of the vicinal quaternary methyl groups present the major challenge in the construction of this subunit. Our first route to (+/-)-12 was marked by low overall yield (<2%) and the instability of several key intermediates; these deficiencies were rectified in a second-generation approach that produced optically active material (18 steps from 19a, 2.1% overall). The successful strategies exploited enolate generation via either conjugate additions to alpha,beta-enones or the Evans oxy-Cope rearrangement as key regiochemical control elements.