dimethyl trans-1-isopropyl-4-methylbicyclo[2.2.2]octane-2,3-dicarboxylate

• 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: dimethyl trans-1-isopropyl-4-methylbicyclo[2.2.2]octane-2,3-dicarboxylate
• 化学式: C₁₆H₂₆O₄
• 分子量: 282.38
• InChiKey: JMXSZLLQSXEEAP-GVAFMPQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  dimethyl trans-1-isopropyl-4-methylbicyclo[2.2.2]octane-2,3-dicarboxylate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 4.0h， 以80%的产率得到trans-(1-isopropyl-4-methylbicyclo[2.2.2]octane-2,3-diyl)dimethanol
  参考文献：
  名称：

  Synthesis of methyl β-alkylcarboxylates by Pd/diphosphine-catalyzed methoxycarbonylation of methylenealkanes RCH2CH2C(R)=CH2

  摘要：

  A series of methylenealkanes RCH2CH2(R)C = CH2 (R = n-butyl, n-hexyl, isopropyl and isobutyl), which are products of selective zirconocene-catalyzed dimerization of alpha-olefins, were introduced into Pd-catalyzed methoxycarbonylation. With the use of 5-methyleneundecane (1-hexene dimer) as a substrate, the roles of protic acid, Lewis acid and molecular hydrogen were established for model Pd(ll)/PPh3 and Pd(II)/diphosphine catalysts.A series of bridged diphosphines were studied as catalyst components L in PdCl2/L-catalyzed methoxycarbonylation in the presence of H-2. One of the nine diphosphines studied, trans-2,3-bis(diphenylphosphinomethyl)norbomane, demonstrated the best catalytic results in terms of catalytic activity, selectivity and isolated yields of the products. Under the optimized conditions during 24 h experiments, dimers RCH2CH2(R)C = CH2 were transformed to methyl carboxylates RCH2CH2(R)CHCH2COOMe with 99 +% regioselectivity; isolated yields were 62-81%.In that way, the catalytic methoxycarbonylation of synthetically available methylenealkanes is an effective approach to branched carboxylic acids, with high prospects for practical application.

  DOI：

  10.1016/j.apcata.2019.05.030
• 作为产物：
  描述：

  松油烯 在 5%-palladium/activated carbon 作用下， 以 甲醇 为溶剂， 反应 22.0h， 生成 dimethyl trans-1-isopropyl-4-methylbicyclo[2.2.2]octane-2,3-dicarboxylate
  参考文献：
  名称：

  Synthesis of methyl β-alkylcarboxylates by Pd/diphosphine-catalyzed methoxycarbonylation of methylenealkanes RCH2CH2C(R)=CH2

  摘要：

  A series of methylenealkanes RCH2CH2(R)C = CH2 (R = n-butyl, n-hexyl, isopropyl and isobutyl), which are products of selective zirconocene-catalyzed dimerization of alpha-olefins, were introduced into Pd-catalyzed methoxycarbonylation. With the use of 5-methyleneundecane (1-hexene dimer) as a substrate, the roles of protic acid, Lewis acid and molecular hydrogen were established for model Pd(ll)/PPh3 and Pd(II)/diphosphine catalysts.A series of bridged diphosphines were studied as catalyst components L in PdCl2/L-catalyzed methoxycarbonylation in the presence of H-2. One of the nine diphosphines studied, trans-2,3-bis(diphenylphosphinomethyl)norbomane, demonstrated the best catalytic results in terms of catalytic activity, selectivity and isolated yields of the products. Under the optimized conditions during 24 h experiments, dimers RCH2CH2(R)C = CH2 were transformed to methyl carboxylates RCH2CH2(R)CHCH2COOMe with 99 +% regioselectivity; isolated yields were 62-81%.In that way, the catalytic methoxycarbonylation of synthetically available methylenealkanes is an effective approach to branched carboxylic acids, with high prospects for practical application.

  DOI：

  10.1016/j.apcata.2019.05.030

文献信息

• Synthesis of methyl β-alkylcarboxylates by Pd/diphosphine-catalyzed methoxycarbonylation of methylenealkanes RCH2CH2C(R)=CH2
  作者：Ilya E. Nifant’ev、Nadezhda T. Sevostyanova、Sergey A. Batashev、Alexey A. Vinogradov、Alexander A. Vinogradov、Andrei V. Churakov、Pavel V. Ivchenko

  DOI：10.1016/j.apcata.2019.05.030

  日期：2019.7

  A series of methylenealkanes RCH2CH2(R)C = CH2 (R = n-butyl, n-hexyl, isopropyl and isobutyl), which are products of selective zirconocene-catalyzed dimerization of alpha-olefins, were introduced into Pd-catalyzed methoxycarbonylation. With the use of 5-methyleneundecane (1-hexene dimer) as a substrate, the roles of protic acid, Lewis acid and molecular hydrogen were established for model Pd(ll)/PPh3 and Pd(II)/diphosphine catalysts.A series of bridged diphosphines were studied as catalyst components L in PdCl2/L-catalyzed methoxycarbonylation in the presence of H-2. One of the nine diphosphines studied, trans-2,3-bis(diphenylphosphinomethyl)norbomane, demonstrated the best catalytic results in terms of catalytic activity, selectivity and isolated yields of the products. Under the optimized conditions during 24 h experiments, dimers RCH2CH2(R)C = CH2 were transformed to methyl carboxylates RCH2CH2(R)CHCH2COOMe with 99 +% regioselectivity; isolated yields were 62-81%.In that way, the catalytic methoxycarbonylation of synthetically available methylenealkanes is an effective approach to branched carboxylic acids, with high prospects for practical application.