8-tert-butyl-1,4-dioxaspiro[4.5]decan-6-one | 175286-33-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 8-tert-butyl-1,4-dioxaspiro[4.5]decan-6-one
• CAS: 175286-33-6
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: WMOSXBXSLZYNFN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  8-tert-butyl-1,4-dioxaspiro[4.5]decan-6-one 在 盐酸 、 indium 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 水 、 丙酮 为溶剂， 反应 51.5h， 生成 (1R*,2R*,4R*)-1-allyl-4-tert-butyl-2-methoxycyclohexanol
  参考文献：
  名称：

  Evaluation of Chelation Effects Operative during Diastereoselective Addition of the Allylindium Reagent to 2- and 3-Hydroxycyclohexanones in Aqueous, Organic, and Mixed Solvent Systems

  摘要：

  The unprotected 2- and 3-hydroxycyclohexanones 1-8 were prepared by methods that skirted as much as possible their proclivity for alpha-ketol rearrangement (where the possibility for such isomerization exists). The diastereofacial selectivity of their reaction with the allylindium reagent in water, 50% aqueous THF, and anhydrous THF is described. The neighboring alpha-hydroxyl substituent is construed to be capable of engaging in chelation, thereby controlling the stereochemical outcome of the coupling process. When the hydroxyl substituent is oriented in the equatorial plane, kinetic acceleration accompanies exclusive entry of the allyl group from the equatorial direction. Steric congestion in the vicinity of the binding hydroxyl and ketonic centers is well tolerated. Alternative projection of the OH group into the more crowded axial region may not curtail chelation. For coordination to occur, however, a twist-boat conformation must initially be adopted. While the evidence suggests that this may indeed occur in water, the necessity of crossing the added energy barrier precludes the attainment of rates that are competitive with those exhibited by the equatorial epimers (competition experiments). Placement of the hydroxyl group at C-3 provides no evident opportunity for chelation control. However, excellent stereoselectivity is seen upon axial orientation of the 3-OH group. This phenomenon is attributed to steric and/or electronic effects alone or in combination.

  DOI：

  10.1021/jo980974y
• 作为产物：
  描述：

  4-叔丁基环己酮 在 吡啶 、 二甲基硫 、 对甲苯磺酸 、 臭氧 、 三乙胺 、 lithium diisopropyl amide 、 原甲酸三甲酯 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 6.0h， 生成 8-tert-butyl-1,4-dioxaspiro[4.5]decan-6-one
  参考文献：
  名称：

  烯丙基金属试剂向 2-甲氧基环己酮和四氢呋喃螺-（2-环己酮）的 1,2-加成中的 π-面非对映选择

  摘要：

  已经确定了几种烯丙基金属试剂和 Normant Grignard [ClMgO(CH2)3MgCl] 的 1,2-加成到 2-甲氧基环己酮和四氢呋喃螺-(2-环己酮) 的立体化学过程。在检测的六种底物中的四种中，存在一个 4-叔丁基作为构象锚。相邻的甲氧基取代基显示出能够有效参与螯合，尽管特殊情况可能另有规定。涉及烯丙基试剂作为水溶液中的亲核试剂的实验表明，水的存在不会抑制螯合控制的操作，这通常大大超过在无水介质中使用相应的镁、铈和铬试剂所能达到的效果。

  DOI：

  10.1021/ja9536835