2,2-dimethyl-propionic acid 6-isopropylidene-5-oxo-3-triisopropylsilanyloxymethylcyclohex-1-enyl ester | 1275615-77-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,2-dimethyl-propionic acid 6-isopropylidene-5-oxo-3-triisopropylsilanyloxymethylcyclohex-1-enyl ester
• 英文别名: [5-Oxo-6-propan-2-ylidene-3-[tri(propan-2-yl)silyloxymethyl]cyclohexen-1-yl] 2,2-dimethylpropanoate
• CAS: 1275615-77-4
• 化学式: C₂₄H₄₂O₄Si
• 分子量: 422.681
• InChiKey: LAFKVAJRTYCFAB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.58
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  一氧化碳 、 2,2-dimethyl-propionic acid 1,1-dimethyl-3-(2-triisopropylsilanyloxymethylcyclopropyl)-prop-2-ynyl ester 在 di(rhodium)tetracarbonyl dichloride 作用下， 以 甲苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 5.0h， 以93%的产率得到2,2-dimethyl-propionic acid 6-isopropylidene-5-oxo-3-triisopropylsilanyloxymethylcyclohex-1-enyl ester
  参考文献：
  名称：

  Rhodium-Catalyzed Carbonylation of Cyclopropyl Substituted Propargyl Esters: A Tandem 1,3-Acyloxy Migration [5 + 1] Cycloaddition

  摘要：

  We have developed two different types of tandem reactions for the synthesis of highly functionalized cyclohexenones from cyclopropyl substituted propargyl esters. Both reactions were initiated by rhodium-catalyzed Saucy-Marbet 1,3-acyloxy migration. The resulting cyclopropyl substituted allenes derived from acyloxy migration then underwent [5 + 1] cycloaddition with CO. The acyloxy group not only eased the access to allene intermediates but also provided a handle for further selective functionalizations.

  DOI：

  10.1021/jo300973r

文献信息

• Synthesis of Highly Functionalized Cyclohexenone Rings: Rhodium-Catalyzed 1,3-Acyloxy Migration and Subsequent [5+1] Cycloaddition
  作者：Dongxu Shu、Xiaoxun Li、Min Zhang、Patrick J. Robichaux、Weiping Tang

  DOI：10.1002/anie.201006881

  日期：2011.2.7

  from cyclopropyl‐substituted propargyl esters by using a [Rh(CO)2Cl}2] catalyst. This metal catalyst promoted the 1,3‐acyloxy migration of propargyl esters and a subsequent [5+1] cycloaddition of the resulting allenylcyclopropanes in the presence of CO with high regioselectivity.

  Lead Rh-ole：通过使用 [Rh(CO) 2 Cl} 2 ] 催化剂，由环丙基取代的炔丙酯制备高度取代的环己烯酮。这种金属催化剂在 CO 存在下促进了炔丙酯的 1,3-酰氧基迁移和随后得到的烯丙基环丙烷的 [5+1] 环加成反应，具有高区域选择性。