(1S,5R)-1-(tert-Butyl-diphenyl-silanyloxymethyl)-spiro[4.5]deca-2,6-dien-8-one | 226546-05-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,5R)-1-(tert-Butyl-diphenyl-silanyloxymethyl)-spiro[4.5]deca-2,6-dien-8-one
• 英文别名: (4S,5R)-4-[[tert-butyl(diphenyl)silyl]oxymethyl]spiro[4.5]deca-2,9-dien-8-one
• CAS: 226546-05-0
• 化学式: C₂₇H₃₂O₂Si
• 分子量: 416.635
• InChiKey: QGBVOSBKBQUNBL-AJTFRIOCSA-N

物化性质

• 沸点：
  509.402±50.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.087±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.04
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,5R)-1-(tert-Butyl-diphenyl-silanyloxymethyl)-spiro[4.5]deca-2,6-dien-8-one 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以85%的产率得到(1S,5R)-1-Hydroxymethyl-spiro[4.5]deca-2,6-dien-8-one
  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：

  (E)-4-(tert-butyldiphenylsilyloxy)-2-buten-1-ol 在 N-溴代丁二酰亚胺(NBS) 、 Grubbs catalyst first generation 、 二甲基硫 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 5.0h， 生成 (1S,5R)-1-(tert-Butyl-diphenyl-silanyloxymethyl)-spiro[4.5]deca-2,6-dien-8-one
  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.