(3R,6S,8aS)-6-[(2R)-1-[tert-butyl(diphenyl)silyl]oxybut-3-en-2-yl]-2,2,8a-trimethyl-3-phenyl-6-prop-2-enyl-7,8-dihydro-3H-[1,3]oxazolo[3,2-a]pyridine-5-thione | 226546-08-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (3R,6S,8aS)-6-[(2R)-1-[tert-butyl(diphenyl)silyl]oxybut-3-en-2-yl]-2,2,8a-trimethyl-3-phenyl-6-prop-2-enyl-7,8-dihydro-3H-[1,3]oxazolo[3,2-a]pyridine-5-thione
• CAS: 226546-08-3
• 化学式: C₃₉H₄₉NO₂SSi
• 分子量: 623.975
• InChiKey: CZMOINIVGMATKD-RRKASHIISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.62
• 重原子数：
  44
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  53.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R,6S,8aS)-6-[(2R)-1-[tert-butyl(diphenyl)silyl]oxybut-3-en-2-yl]-2,2,8a-trimethyl-3-phenyl-6-prop-2-enyl-7,8-dihydro-3H-[1,3]oxazolo[3,2-a]pyridine-5-thione 在 (PCy₃)2Ru=CHPh 、 triethyloxonium fluoroborate 、 红铝 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  An Asymmetric Route to Novel Chiral Cyclohexenones with Spiro-Connected Cyclopentenes. Further Utility of Chiral Bicyclic Thiolactams and the [3,3] Thio-Claisen Products

  摘要：

  Sequential allylation of chiral, nonracemic thiolactam 8 affords clean thio-Claisen [3,3] products ii. The stereoselectivity of the rearrangement was found to be on the order of 10-11:1, with the exo-endo products responsible for the mixture. Addition of hydride or methyllithium-cerium chloride gave clean addition to the thiolactam in the form of its iminium salts 12. Hydrolysis gave 4,4-dialkylcyclohexenones 16, which were cyclized to the cyclopentene derivatives 16 using Grubbs' catalyst.

  DOI：

  10.1021/jo982426q
• 作为产物：
  描述：

  (3R,8aS)-2,2,8a-trimethyl-3-phenyl-3,6,7,8-tetrahydro-[1,3]oxazolo[3,2-a]pyridine-5-thione 在 potassium carbonate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 生成 (3R,6S,8aS)-6-[(2R)-1-[tert-butyl(diphenyl)silyl]oxybut-3-en-2-yl]-2,2,8a-trimethyl-3-phenyl-6-prop-2-enyl-7,8-dihydro-3H-[1,3]oxazolo[3,2-a]pyridine-5-thione
  参考文献：
  名称：

  An Asymmetric Route to Novel Chiral Cyclohexenones with Spiro-Connected Cyclopentenes. Further Utility of Chiral Bicyclic Thiolactams and the [3,3] Thio-Claisen Products

  摘要：

  Sequential allylation of chiral, nonracemic thiolactam 8 affords clean thio-Claisen [3,3] products ii. The stereoselectivity of the rearrangement was found to be on the order of 10-11:1, with the exo-endo products responsible for the mixture. Addition of hydride or methyllithium-cerium chloride gave clean addition to the thiolactam in the form of its iminium salts 12. Hydrolysis gave 4,4-dialkylcyclohexenones 16, which were cyclized to the cyclopentene derivatives 16 using Grubbs' catalyst.

  DOI：

  10.1021/jo982426q

文献信息

• An Asymmetric Route to Novel Chiral Cyclohexenones with Spiro-Connected Cyclopentenes. Further Utility of Chiral Bicyclic Thiolactams and the [3,3] Thio-Claisen Products
  作者：René M. Lemieux、Paul N. Devine、Mark F. Mechelke、A. I. Meyers

  DOI：10.1021/jo982426q

  日期：1999.5.1

  Sequential allylation of chiral, nonracemic thiolactam 8 affords clean thio-Claisen [3,3] products ii. The stereoselectivity of the rearrangement was found to be on the order of 10-11:1, with the exo-endo products responsible for the mixture. Addition of hydride or methyllithium-cerium chloride gave clean addition to the thiolactam in the form of its iminium salts 12. Hydrolysis gave 4,4-dialkylcyclohexenones 16, which were cyclized to the cyclopentene derivatives 16 using Grubbs' catalyst.