methyl 3-(p-tolyl)bicyclo<1.1.1>pentyl-1-carboxylate

• 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: methyl 3-(p-tolyl)bicyclo<1.1.1>pentyl-1-carboxylate
• 英文别名: Methyl 3-(4-methylphenyl)bicyclo[1.1.1]pentane-1-carboxylate；methyl 3-(4-methylphenyl)bicyclo[1.1.1]pentane-1-carboxylate
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: FAQXANSIEVKJNF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,3-二碘双环[1.1.1]戊烷 在 氢氧化钾 、 氯化亚砜 作用下， 以 苯 为溶剂， 反应 28.5h， 生成 methyl 3-(p-tolyl)bicyclo<1.1.1>pentyl-1-carboxylate
  参考文献：
  名称：

  Formation and Reactions of Bicyclo[1.1.1]pentyl-1 Cations

  摘要：

  The ionization of l-bicyclo[1.1.1]pentyl halides was shown to initially form the 1,3-bridged bicycle[1.1.1]pentyl-l cation. It appears to be a transition state that leads to the bicyclo[1.1.0]butyl-1-carbinyl cation which can be trapped with azide ion and can be directly observed by NMR in SO2CIF. Although the major products of solvolysis of the halides are 3-methylenecyclobutyl derivatives, the corresponding cation was calculated to have a significantly higher energy than the bicyclobutylcarbinyl ion. Therefore, the products are probably formed by an attack of the nucleophile on the latter ion, accompanied by bond migration. The bridgehead iodide reacts under solvolytic conditions with azide ion to form bicyclo[1.1.0]butyl-l azide as a product. It also reacts with potassium hydroxide to give [1.1.1]propellane, and the same reaction occurs on dissolving in acetonitrile or pyridine. The reaction of 1,3-diiodobicyclo[1.1.1]pentane with ethoxide ion also was found to give [1.1.1]propellane via a nucleophilic attack on one of the iodines. The propellane reacts with methyl hypoiodite to give 3-iodobicyclo[1.1.1]pentyl-l cation, which can react with methanol to give 3-methoxybicyclo[1.1.1]pentyl-l iodide and with azide ion to give 3-iodobicyclo[1.1.1]pentyl-1 azide. These data provide evidence for a discrete 3-iodobicyclo[1.1.1]pentyl-l cation intermediate. The effect of substituents on the rate of solvolysis of bicyclo[1.1.1]pentyl-l iodide was studied. With 3-aryl substituents, a value of rho = -1.7 was found, which is similar to that observed in the solvolysis of 3-arylcyclobutyl tosylates (rho = -1.6). The 3-substituted bicyclopentyl halides usually form the corresponding 3-methylenecyclobutyl cations rather than bicyclo[1.1.0]butyl-1-carbinyl ions, because most substituents will help stabilize the former type of ion.

  DOI：

  10.1021/ja00105a046

文献信息

• Methods for cross coupling
  申请人：Recurium IP Holdings, LLC

  公开号：US10793504B2

  公开（公告）日：2020-10-06

  Methods of preparing substituted bicyclo[0.1.1.1]pentane compounds of Formula (I) comprise reacting a compound of Formula (A) with a compound of Formula (B) in the presence of a first transition metal catalyst selected from a palladium catalyst and a nickel catalyst, where the variables R1, R2, X1 and X2 are as described herein.

  制备取代的式(I)双环[0.1.1.1]戊烷化合物的方法包括在选自钯催化剂和镍催化剂的第一过渡金属催化剂存在下，使式(A)化合物与式(B)化合物反应，其中变量R1、R2、X1和X2如本文所述。
• METHODS FOR CROSS COUPLING
  申请人：ZENO ROYALTIES & MILESTONES, LLC

  公开号：US20190202769A1

  公开（公告）日：2019-07-04

  Methods of preparing substituted bicyclo[0.1.1.1]pentane compounds of Formula (I) comprise reacting a compound of Formula (A) with a compound of Formula (B) in the presence of a first transition metal catalyst selected from a palladium catalyst and a nickel catalyst, where the variables R 1 , R 2 , X 1 and X 2 are as described herein.
• [EN] METHODS FOR CROSS COUPLING<br/>[FR] PROCÉDÉS DE COUPLAGE CROISÉ
  申请人：KALYRA PHARMACEUTICALS INC

  公开号：WO2018039232A1

  公开（公告）日：2018-03-01

  Methods of preparing substituted bicyclo[1.1.1]pentane compounds of Formula (I) comprise reacting a compound of Formula (A) with a compound of Formula (B) in the presence of a first transition metal catalyst selected from a palladium catalyst and a nickel catalyst, where the variables R1, R2, X1 and X2 are as described herein.