(1R,4S)-2,6,6-trimethyl-2-cyclohexen-1,4-diol | 169272-96-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,4S)-2,6,6-trimethyl-2-cyclohexen-1,4-diol
• 英文别名: (1R,4S)-2,6,6-trimethylcyclohex-2-ene-1,4-diol
• CAS: 169272-96-2
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: GVYFIMKMHDHRLF-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,4S)-2,6,6-trimethyl-2-cyclohexen-1,4-diol 在 咪唑 、 重铬酸吡啶 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 22.0h， 生成 (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone
  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
• 作为产物：
  描述：

  [(1S,4R)-4-hydroxy-3,5,5-trimethylcyclohex-2-en-1-yl] acetate 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 17.0h， 生成 (1R,4S)-2,6,6-trimethyl-2-cyclohexen-1,4-diol
  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

• Methods for the synthesis of astaxanthin
  申请人：Lockwood F. Samuel

  公开号：US20060183947A1

  公开（公告）日：2006-08-17

  A method used for synthesizing intermediates for use in the synthesis of carotenoids and carotenoid analogs, and/or carotenoid derivatives. In some embodiments, the invention includes methods for synthesizing optically active intermediates useful for the synthesis of optically active carotenoids. Synthesis of optically active carotenoids, in one embodiment, may be accomplished by forming an optically active dihydroxy intermediate from ketoisopherone. The optically active dihydroxy intermediate may be converted into optically active astaxanthin derivatives.

  一种用于合成类胡萝卜素和类胡萝卜素类似物以及/或类胡萝卜素衍生物的中间体的方法。在某些实施例中，本发明包括用于合成光学活性类胡萝卜素的光学活性中间体的方法。在一种实施例中，光学活性类胡萝卜素的合成可以通过从酮异苯酮形成光学活性二羟基中间体来完成。光学活性二羟基中间体可以转化为光学活性虾青素衍生物。
• [EN] METHODS FOR SYNTHESIS OF CHIRAL INTERMEDIATES OF CAROTENOIDS, CAROTENOID ANALOGS, AND CAROTENOID DERIVATIVES<br/>[FR] PROCEDES PERMETTANT LA SYNTHESE D'INTERMEDIAIRES CHIRAUX DE CAROTENOIDES, D'ANALOGUES DE CAROTENOIDES ET DE DERIVES DE CAROTENOIDES
  申请人：HAWAII BIOTECH INC

  公开号：WO2006039685A3

  公开（公告）日：2007-01-04
• US7247752B2
  申请人：——

  公开号：US7247752B2

  公开（公告）日：2007-07-24