(4aS,8aS)-(-)-4-bromo-4a,5,6,7,8,8a-hexahydro-1,1,3,6,6-pentamethyl-1H-2-benzopyran | 191656-41-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢呋喃
• 英文名称: (4aS,8aS)-(-)-4-bromo-4a,5,6,7,8,8a-hexahydro-1,1,3,6,6-pentamethyl-1H-2-benzopyran
• 英文别名: (4aS,8aS)-4-bromo-1,1,3,6,6-pentamethyl-5,7,8,8a-tetrahydro-4aH-isochromene
• CAS: 191656-41-4
• 化学式: C₁₄H₂₃BrO
• 分子量: 287.24
• InChiKey: VGZDGWFBDIZVTA-QWRGUYRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.86
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (4aS,8aS)-(-)-4-bromo-4a,5,6,7,8,8a-hexahydro-1,1,3,6,6-pentamethyl-1H-2-benzopyran 在 正丁基锂 、 titanium(III) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 (4aR,8aR)-(+)-4a,5,6,7,8,8a-hexahydro-1,1,3,6,6-pentamethyl-4-(p-toluenesulfenyl)-1H-2-benzopyran
  参考文献：
  名称：

  The Lewis Acid-catalyzed Intramolecular Asymmetric Hetero Diels-Alder Reaction of Chiral a'-Sulfinyl-a,b-unsaturated Ketone. A Chiral Diene Bearing an Optically Active Sulfinylmethyl Group

  摘要：

  This paper presents an asymmetric Diels-Alder reaction with a diene bearing a chiral sulfinyl group. The Lewis acid-catalyzed intramolecular asymmetric hetero Diels-Alder reaction of a chiral alpha'-sulfinyl-alpha,beta-unsaturated ketone derived from 3-methylcitronellal produced optically active 4a,5,6,7,8,8a-hexahydro-1H-2-benzopyran derivatives. On the basis of the stereochemical results obtained, a plausible mechanism for the asymmetric induction is presented.

  DOI：

  10.3987/com-92-s27
• 作为产物：
  描述：

  (4aR,8aS)-4a,5,6,7,8,8a-hexahydro-1,1,6,6-tetramethyl-2-p-toluenesulfinyl-1H-2-benzopyran 在 N-溴代丁二酰亚胺(NBS) 、 sodium 、 异丙醇 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 5.0h， 生成 (4aS,8aS)-(-)-4-bromo-4a,5,6,7,8,8a-hexahydro-1,1,3,6,6-pentamethyl-1H-2-benzopyran
  参考文献：
  名称：

  The Lewis Acid-catalyzed Intramolecular Asymmetric Hetero Diels-Alder Reaction of Chiral a'-Sulfinyl-a,b-unsaturated Ketone. A Chiral Diene Bearing an Optically Active Sulfinylmethyl Group

  摘要：

  This paper presents an asymmetric Diels-Alder reaction with a diene bearing a chiral sulfinyl group. The Lewis acid-catalyzed intramolecular asymmetric hetero Diels-Alder reaction of a chiral alpha'-sulfinyl-alpha,beta-unsaturated ketone derived from 3-methylcitronellal produced optically active 4a,5,6,7,8,8a-hexahydro-1H-2-benzopyran derivatives. On the basis of the stereochemical results obtained, a plausible mechanism for the asymmetric induction is presented.

  DOI：

  10.3987/com-92-s27

文献信息

• Studies on Chiral Organosulfur Compounds. VI. The Use of a Chiral Diene Bearing an Optically Active Sulfinylmethyl Group in the Lewis Acid-Catalyzed Intramolecular Asymmetric Hetero Diels-Alder Reaction.
  作者：Kunio HIROI、Masayuki UMEMURA、Yoko TOMIKAWA、Masamitsu KANEKO、Fumiko KATO

  DOI：10.1248/cpb.45.759

  日期：——

  An asymmetric Diels-Alder reaction with a diene bearing a chiral sulfinyl group is described. The Lewis acid-catalyzed intramolecular asymmetric hetero Diels-Alder reaction of a chiral α'-sulfinyl-α, β-unsaturated ketone derived from 3-methylcitronellal produced optically active 4a, 5, 6, 7, 8, 8a-hexahydro-1H-2-benzopyran derivatives. On the basis of the stereochemical results obtained, a plausible mechanism for the asymmetric induction is presented.

  描述了一种带有手性亚磺酰基的二烯的不对称 Diels-Alder 反应。在路易斯酸催化下，由 3-甲基香茅醛衍生的手性 α'-亚磺酰基-α, β-不饱和酮发生了分子内不对称杂化 Diels-Alder 反应，生成了具有光学活性的 4a、5、6、7、8、8a-六氢-1H-2-苯并吡喃衍生物。根据所获得的立体化学结果，提出了不对称诱导的合理机制。