(1R,4R)-4-tert-Butyl-2-[1-phenyl-meth-(E)-ylidene]-cyclohexanol | 75910-63-3

• 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: (1R,4R)-4-tert-Butyl-2-[1-phenyl-meth-(E)-ylidene]-cyclohexanol
• 英文别名: (1R,2E,4R)-2-benzylidene-4-tert-butylcyclohexan-1-ol
• CAS: 75910-63-3
• 化学式: C₁₇H₂₄O
• 分子量: 244.377
• InChiKey: QTHNQKXHBPWJEW-GSEJNISDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.28
• 重原子数：
  18.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (1R,4R)-4-tert-Butyl-2-[1-phenyl-meth-(E)-ylidene]-cyclohexanol 在 咪唑 、 二甲基硫 、 臭氧 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成
  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：

  6-((E)-benzylidene)-8-tert-butyl-1,4-dioxaspiro[4.5]decane 在 盐酸 、 Lithium-tri-methoxy-alanat 作用下， 生成 (1R,4R)-4-tert-Butyl-2-[1-phenyl-meth-(E)-ylidene]-cyclohexanol
  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

文献信息

• Sanghvi, Y. S.; Rao, A. S., Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1980, vol. 19, # 7, p. 608 - 610
  作者：Sanghvi, Y. S.、Rao, A. S.

  DOI：——

  日期：——
• Sanghvi, Y. S.; Rao, A. S., Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1987, vol. 26, p. 671 - 673
  作者：Sanghvi, Y. S.、Rao, A. S.

  DOI：——

  日期：——
• SANOHVI Y. S.; RAO A. S., INDIAN J. CHEM., 1980, B19, NO 7, 608-610
  作者：SANOHVI Y. S.、 RAO A. S.

  DOI：——

  日期：——
• SANGHVI, Y. S.;RAO, A. S., INDIAN J. CHEM., 26,(1987) N 6, 671-673
  作者：SANGHVI, Y. S.、RAO, A. S.

  DOI：——

  日期：——