(1S,3R,6R,8S)-1,2,3,6,7,8-hexahydro-2,2,7,7-tetramethyl-1,3:6,8-dimethanophenanthrene-4,5-dione (E,E)-bis(O-methyloxime) | 251096-37-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (1S,3R,6R,8S)-1,2,3,6,7,8-hexahydro-2,2,7,7-tetramethyl-1,3:6,8-dimethanophenanthrene-4,5-dione (E,E)-bis(O-methyloxime)
• 英文别名: (1S,6S,8R,13R)-9-N,12-N-dimethoxy-7,7,14,14-tetramethylpentacyclo[11.1.1.16,8.02,11.05,10]hexadeca-2(11),3,5(10)-triene-9,12-diimine
• CAS: 251096-37-4
• 化学式: C₂₂H₂₈N₂O₂
• 分子量: 352.477
• InChiKey: YICARJNFPDUPHV-HRCNURNJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,3R,6R,8S)-1,2,3,6,7,8-hexahydro-2,2,7,7-tetramethyl-1,3:6,8-dimethanophenanthrene-4,5-dione (E,E)-bis(O-methyloxime) 在 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 、 二乙二醇二甲醚 为溶剂， 反应 120.0h， 以83%的产率得到(1S,3R,4S,5S,6R,8S)-1,2,3,4,5,6,7,8-octahydro-2,2,7,7-tetramethyl-1,3:6,8-dimethanophenanthrene-4,5-diamine
  参考文献：
  名称：

  Synthesis of Enantiopure C₂-Symmetric VERDI Disulfonamides and Their Application to the Catalytic Enantioselective Addition of Diethylzinc to Aromatic and Aliphatic Aldehydes

  摘要：

  The enantiopure disulfonamides 7a-c have been prepared from the Ct-symmetric diketone 2, a starting material conveniently accessible from the "dimerization" of (+)-verbenone. These ligands, when treated with titanium isopropoxide and diethylzinc, function as catalysts for the enantioselective alkylation of aldehydes. Stereoselectivity levels ranging from 72 to 98% ee are seen depending on the structural characteristics of the aldehyde. In all cases, the absolute configuration of the carbinol product is R. A working mechanistic model is advanced for the purpose of rationalizing the high levels and direction of asymmetric induction exhibited by these VERDI catalysts.

  DOI：

  10.1021/jo990984e
• 作为产物：
  描述：

  (1S,3R,6R,8S)-1,2,3,6,7,8-Hexahydro-2,2,7,7-tetramethyl-1,3:6,8-dimethanophenathrene-4,5-dione 在 吡啶 作用下， 以 甲醇 、 氘代氯仿 为溶剂， 生成 (1S,3R,6R,8S)-1,2,3,6,7,8-hexahydro-2,2,7,7-tetramethyl-1,3:6,8-dimethanophenanthrene-4,5-dione (E,E)-bis(O-methyloxime)
  参考文献：
  名称：

  Synthesis of Enantiopure C₂-Symmetric VERDI Disulfonamides and Their Application to the Catalytic Enantioselective Addition of Diethylzinc to Aromatic and Aliphatic Aldehydes

  摘要：

  The enantiopure disulfonamides 7a-c have been prepared from the Ct-symmetric diketone 2, a starting material conveniently accessible from the "dimerization" of (+)-verbenone. These ligands, when treated with titanium isopropoxide and diethylzinc, function as catalysts for the enantioselective alkylation of aldehydes. Stereoselectivity levels ranging from 72 to 98% ee are seen depending on the structural characteristics of the aldehyde. In all cases, the absolute configuration of the carbinol product is R. A working mechanistic model is advanced for the purpose of rationalizing the high levels and direction of asymmetric induction exhibited by these VERDI catalysts.

  DOI：

  10.1021/jo990984e

文献信息

• Synthesis of Enantiopure <i>C</i>₂-Symmetric VERDI Disulfonamides and Their Application to the Catalytic Enantioselective Addition of Diethylzinc to Aromatic and Aliphatic Aldehydes
  作者：Leo A. Paquette、Renjie Zhou

  DOI：10.1021/jo990984e

  日期：1999.10.1

  The enantiopure disulfonamides 7a-c have been prepared from the Ct-symmetric diketone 2, a starting material conveniently accessible from the "dimerization" of (+)-verbenone. These ligands, when treated with titanium isopropoxide and diethylzinc, function as catalysts for the enantioselective alkylation of aldehydes. Stereoselectivity levels ranging from 72 to 98% ee are seen depending on the structural characteristics of the aldehyde. In all cases, the absolute configuration of the carbinol product is R. A working mechanistic model is advanced for the purpose of rationalizing the high levels and direction of asymmetric induction exhibited by these VERDI catalysts.