6-(5-hydroxy-3-oxopentyl)-4,4,6-trimethylcyclohex-2-en-1-one | 403483-57-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-(5-hydroxy-3-oxopentyl)-4,4,6-trimethylcyclohex-2-en-1-one
• CAS: 403483-57-8
• 化学式: C₁₄H₂₂O₃
• 分子量: 238.327
• InChiKey: JFBUZNJXJGODSS-UHFFFAOYSA-N

物化性质

• 沸点：
  371.0±25.0 °C(Predicted)
• 密度：
  1.014±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.28
• 重原子数：
  17.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  54.37
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  6-(5-hydroxy-3-oxopentyl)-4,4,6-trimethylcyclohex-2-en-1-one 在 sodium methylate 作用下， 以 甲醇 、 苯 为溶剂， 反应 2.0h， 以72%的产率得到1-Hydroxymethyl-4a,6,6-trimethyl-4,4a,5,6-tetrahydro-3H-naphthalen-2-one
  参考文献：
  名称：

  Formal Synthesis of (±)-Guanacastepene A

  摘要：

  A 17 step synthesis of 55, a late intermediate in Danishefsky's guanacastepene A synthesis, has been completed in 4% overall yield. Key features include the use of vinylmagnesium bromide in the Pd-catalyzed coupling with triflate 13 to give triene 16 without the formation of Heck products, a novel extension of the Stork-Jung vinylsilane Robinson annulation that provides tricyclic 2-hydroxymethylcyclohexenone 42 from 23b in four steps and 51% yield, the ability to obtain almost exclusively alpha'-alkylation of 35ba by the proper choice of protecting groups, and the ability to obtain the desired -alcohol selectively by reduction of keto alcohol 42 rather than keto ester 53.

  DOI：

  10.1021/jo026702j
• 作为产物：
  描述：

  4,4,6-三甲基环己-2-烯-1-酮 在 N,N-二甲基丙烯基脲 、 py*(HF)x 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 生成 6-(5-hydroxy-3-oxopentyl)-4,4,6-trimethylcyclohex-2-en-1-one
  参考文献：
  名称：

  Formal Synthesis of (±)-Guanacastepene A

  摘要：

  A 17 step synthesis of 55, a late intermediate in Danishefsky's guanacastepene A synthesis, has been completed in 4% overall yield. Key features include the use of vinylmagnesium bromide in the Pd-catalyzed coupling with triflate 13 to give triene 16 without the formation of Heck products, a novel extension of the Stork-Jung vinylsilane Robinson annulation that provides tricyclic 2-hydroxymethylcyclohexenone 42 from 23b in four steps and 51% yield, the ability to obtain almost exclusively alpha'-alkylation of 35ba by the proper choice of protecting groups, and the ability to obtain the desired -alcohol selectively by reduction of keto alcohol 42 rather than keto ester 53.

  DOI：

  10.1021/jo026702j

文献信息

• A novel extension of the Stork–Jung vinylsilane Robinson annelation procedure for the introduction of the cyclohexene of guanacastepene
  作者：Barry B Snider、Bo Shi

  DOI：10.1016/s0040-4039(01)02026-3

  日期：2001.12

  has been developed in a model system to introduce the cyclohexene ring of guanacastepene. Cyclohexenone 16 is prepared by sequential methylation and alkylation with allylic iodide 15. One-pot epoxidation, protodesilylation and hydrolysis of the THP forms dione 19, which cyclizes with NaOMe to 24 in 57% overall yield. Reduction, Mitsunobu inversion, and selective oxidation of the primary alcohol forms

  在模型系统中开发了一种新的脱嵌程序，以引入胍卡斯蒂芬的环己烯环。环己烯酮16是通过顺序甲基化和与烯丙基碘15烷基化制备的。THP的一锅环氧化，原去甲硅烷基化和水解形成二酮19，该二酮与NaOMe环化成24，收率为57％。伯醇的还原，Mitsunobu转化和选择性氧化形成模型29。苯基二甲基甲硅烷基烯丙基碘化物36比Stork使用的三甲基甲硅烷基烯丙基碘化物6更容易制造且更稳定。