(+/-)-4-Hydroxy-3,3,5-trimethyl-2-cyclohexen-1-yl acetate | 128035-99-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (+/-)-4-Hydroxy-3,3,5-trimethyl-2-cyclohexen-1-yl acetate
• 英文别名: (4-hydroxy-3,5,5-trimethylcyclohex-2-en-1-yl) acetate
• CAS: 128035-99-4
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: MFLWAVOTNVNBHO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.66
• 重原子数：
  14.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  2,6,6-三甲基-2-环己烯-1,4-二酮 在 sodium tetrahydroborate 、 cerium(III) chloride 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 18.0h， 生成 (+/-)-4-Hydroxy-3,3,5-trimethyl-2-cyclohexen-1-yl acetate
  参考文献：
  名称：

  Lipase-catalyzed asymmetric synthesis of (R)- and (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone and their dihydro derivatives

  摘要：

  Racemic 4-hydroxy-2,6,6-trimethyl-2-cyclohexenon trans- and cis-2,6,6-trimethyl-2-cyclohexene-1,4-diols were prepared by reduction of 4-oxoisophorone with sodium borohydride-cerium chloride. Lipase (PS-30)-catalyzed kinetic resolution of (+/-)-cis-2,6,6-trimethyl-2-cyclohexene-1,4-diol with vinyl acetate led to (1R, 4S)-4-acetoxy-2,6, 6-trimethyl-2-cyclohexen-1-ol (81 %ee);and (1S, 4K)-1-acetoxy-2,6,6-trimethyl-2-cyclohexene-4-ol (92 %ee). Hydrolysis of the former monoacetate and recrytallization of the resulting material afforded enantiomerically pure (1R, 4S)-2,6,6-trimethyl-2-cyclohexene-1,4-diol. On the other hand, recrystallization of (1S, 4R) monoacetate itself provided an optically pure sample, which was then hydrolyzed to give (1S, 417)-2,6,6-trimethylcyclohexene-1,4-diol. Transformation of both diols into (S)- and (R)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone was conducted in two steps including silylation and oxidation. Catalytic hydrogenation of these (S)- and(R)-silyloxy enones dyer Raney nickel afforded the corresponding dihydro derivatives.

  DOI：

  10.1016/0957-4166(95)00159-m

文献信息

• Oritani, Takayuki; Yamamoto, Hiroshi; Yamashita, Kyohei, Agricultural and Biological Chemistry, 1990, vol. 54, # 1, p. 125 - 130
  作者：Oritani, Takayuki、Yamamoto, Hiroshi、Yamashita, Kyohei

  DOI：——

  日期：——
• ORITANI, TAKAYUKI;YAMAMOTO, HIROSHI;YAMASHITA, EYOHEI, AGR. AND BIOL. CHEM. , 54,(1990) N, C. 125-130
  作者：ORITANI, TAKAYUKI、YAMAMOTO, HIROSHI、YAMASHITA, EYOHEI

  DOI：——

  日期：——
• Lipase-catalyzed asymmetric synthesis of (R)- and (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone and their dihydro derivatives
  作者：Akira Tanaka、Hiroshi Yamamoto、Takayuki Oritani

  DOI：10.1016/0957-4166(95)00159-m

  日期：1995.6

  Racemic 4-hydroxy-2,6,6-trimethyl-2-cyclohexenon trans- and cis-2,6,6-trimethyl-2-cyclohexene-1,4-diols were prepared by reduction of 4-oxoisophorone with sodium borohydride-cerium chloride. Lipase (PS-30)-catalyzed kinetic resolution of (+/-)-cis-2,6,6-trimethyl-2-cyclohexene-1,4-diol with vinyl acetate led to (1R, 4S)-4-acetoxy-2,6, 6-trimethyl-2-cyclohexen-1-ol (81 %ee);and (1S, 4K)-1-acetoxy-2,6,6-trimethyl-2-cyclohexene-4-ol (92 %ee). Hydrolysis of the former monoacetate and recrytallization of the resulting material afforded enantiomerically pure (1R, 4S)-2,6,6-trimethyl-2-cyclohexene-1,4-diol. On the other hand, recrystallization of (1S, 4R) monoacetate itself provided an optically pure sample, which was then hydrolyzed to give (1S, 417)-2,6,6-trimethylcyclohexene-1,4-diol. Transformation of both diols into (S)- and (R)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone was conducted in two steps including silylation and oxidation. Catalytic hydrogenation of these (S)- and(R)-silyloxy enones dyer Raney nickel afforded the corresponding dihydro derivatives.