(4aS,8aS,S_S)-4a,5,6,7,8,8a-hexahydro-1,1,3,6,6-pentamethyl-4-(p-toluenesulfinyl)-1H-2-benzopyran | 145627-31-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (4aS,8aS,S_S)-4a,5,6,7,8,8a-hexahydro-1,1,3,6,6-pentamethyl-4-(p-toluenesulfinyl)-1H-2-benzopyran
• 英文别名: (4aS,8aS,Ss)-(-)-4a,5,6,7,8,8a-hexahydro-1,1,3,6,6-pentamethyl-4-p-toluenesulfinyl-1H-2-benzopyran；(4aS,8aS)-1,1,3,6,6-pentamethyl-4-[(S)-(4-methylphenyl)sulfinyl]-5,7,8,8a-tetrahydro-4aH-isochromene
• CAS: 145627-31-2
• 化学式: C₂₁H₃₀O₂S
• 分子量: 346.534
• InChiKey: DOHOTOCNNXGASM-XFAGBWLFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4aS,8aS,S_S)-4a,5,6,7,8,8a-hexahydro-1,1,3,6,6-pentamethyl-4-(p-toluenesulfinyl)-1H-2-benzopyran 在 titanium(III) chloride 作用下， 生成 (4aS,8aS)-(-)-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：

  带有手性亚磺酰基的二烯的分子内路易斯酸催化的不对称杂Diels-Alder反应

  摘要：

  手性α-亚磺酰基α，β-不饱和酮在分子内路易斯酸催化的不对称环加成反应中用作手性二烯，在某些情况下提供杂-Diels-Alder反应产物以及高光学产率的烯类反应产物。取决于所使用的路易斯酸，容易控制Diels-Alder或烯反应的反应途径。

  DOI：

  10.1016/s0040-4039(00)60862-6
• 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) 、 正丁基锂 、 sodium 、 异丙醇 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 7.0h， 生成 (4aS,8aS,S_S)-4a,5,6,7,8,8a-hexahydro-1,1,3,6,6-pentamethyl-4-(p-toluenesulfinyl)-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. III. Lewis Acid-Catalyzed Intramolecular Asymmetric Pericyclic Reactions of Chiral .ALPHA.-Acetyl and Methoxycarbonylvinylic Sulfoxides.
  作者：Kunio HIROI、Masayuki UMEMURA、Aki FUJISAWA

  DOI：10.1248/cpb.41.666

  日期：——

  A chiral α-sulfinyl α, β-unsaturated ketone served as a good chiral diene or enophile in intramolecular Lewis acid-catalyzed asymmetric pericyclic reactions, giving hetero-Diels-Alder reaction products, together with ene reaction products in some cases, in high optical yields. The reaction pathways for Diels-Alder or ene reactions were readily controlled depending on the Lewis acids used. A chiral α-sulfinyl α, β-unsaturated ester served as a good enophile to give ene reaction products with high enantioselectivity. The mechanistic pathway for the asymmetric induction is proposed on the basis of the stereochemical results obtained.

  一种手性的α-亚磺酰基α,β-不饱和酮在分子内路易斯酸催化的不对称周环反应中作为良好的手性二烯或亲烯，生成异源的Diels-Alder反应产物，以及在某些情况下的烯反应产物，且具有高光学产率。Diels-Alder或烯反应的反应途径可以根据所使用的路易斯酸进行有效控制。一种手性的α-亚磺酰基α,β-不饱和酯作为良好的亲烯，生成具有高对映选择性的烯反应产物。基于获得的立体化学结果，提出了不对称诱导的机制路径。
• Intramolecular Lewis acid-catalyzed asymmetric hetero-Diels-Alder reactions with dienes bearing chiral sulfinyl groups
  作者：Kunio Hiroi、Masayuki Umemura、Aki Fujisawa

  DOI：10.1016/s0040-4039(00)60862-6

  日期：1992.11

  A chiral α-sulfinyl α,β-unsaturated ketone served as a chiral diene in intramolecular Lewis acid-catalyzed asymmetric cycloaddition reactions, giving hetero-Diels-Alder reaction products along in some cases with ene reaction products in high optical yields. The reaction pathways for Diels-Alder or ene reactions were readily controlled depending on the Lewis acids used.

  手性α-亚磺酰基α，β-不饱和酮在分子内路易斯酸催化的不对称环加成反应中用作手性二烯，在某些情况下提供杂-Diels-Alder反应产物以及高光学产率的烯类反应产物。取决于所使用的路易斯酸，容易控制Diels-Alder或烯反应的反应途径。
• 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。
• 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
  作者：Kunio Hiroi、Masayuki Umemura、Yoko Tomikawa

  DOI：10.3987/com-92-s27

  日期：——

  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.