(3R^*,4R^*)-4-(1,1-dimethylethyl)-3-hydroxycyclohexanone | 113778-48-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3R^*,4R^*)-4-(1,1-dimethylethyl)-3-hydroxycyclohexanone
• 英文别名: (3S,4S)-4-tert-butyl-3-hydroxycyclohexan-1-one
• CAS: 113778-48-6
• 化学式: C₁₀H₁₈O₂
• 分子量: 170.252
• InChiKey: PWJVLZVXBUMZRP-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R^*,4R^*)-4-(1,1-dimethylethyl)-3-hydroxycyclohexanone 在 indium 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 13.5h， 生成 (1R*,5S*,6S*)-1-allyl-6-tert-butyl-3,3-dimethyl-2,4-dioxabicyclo[3.3.1]nonane
  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-(1,1-dimethylethyl)cyclohex-3-en-1-one ethylene ketal 在 重铬酸吡啶 、 dimethyl sulfide borane 、 三氟乙酸吡啶 、 L-Selectride 、 溶剂黄146 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 32.0h， 生成 (3R^*,4R^*)-4-(1,1-dimethylethyl)-3-hydroxycyclohexanone
  参考文献：
  名称：

  使用四甲基三乙酰氧基硼氢化铵直接还原 β-羟基酮

  摘要：

  温和的还原剂四甲基铵三乙酰氧基硼氢化物以高非对映选择性将无环 P-羟基酮还原为其相应的反二醇。α-烷基取代不会显着影响这些还原的立体选择性。在所有检查的情况下，都获得了良好到极好的非对映异构体均质二醇的产率。这些还原的机制涉及三乙酰氧基硼氢化物阴离子将乙酸盐与底物醇进行酸促进的配体交换。所得氢化物中间体，大概是烷氧基二乙酰氧基硼氢化物，还原近端 OH 0 OH OH 0 Me,NHB(OAc), Mew Me&OR - OR Me he

  DOI：

  10.1021/ja00219a035

文献信息

• Van Martin; Murray, Desmond H.; Pratt, Norman E., Journal of the American Chemical Society, 1990, vol. 112, # 19, p. 6965 - 6978
  作者：Van Martin、Murray, Desmond H.、Pratt, Norman E.、Zhao, Yun-Bo、Albizati, Kim F.

  DOI：——

  日期：——