di-tert-butyl 2,2-bis(4-(tert-butyl)benzyl)malonate | 1447797-43-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: di-tert-butyl 2,2-bis(4-(tert-butyl)benzyl)malonate
• 英文别名: Ditert-butyl 2,2-bis[(4-tert-butylphenyl)methyl]propanedioate；ditert-butyl 2,2-bis[(4-tert-butylphenyl)methyl]propanedioate
• CAS: 1447797-43-4
• 化学式: C₃₃H₄₈O₄
• 分子量: 508.742
• InChiKey: LSZIQYPCFUVQTI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  37
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  di-tert-butyl 2,2-bis(4-(tert-butyl)benzyl)malonate 在 N,N,N',N'-tetramethyl-7,8-dihydro-6H-dipyrido[1,2-a;2',1'-c][1,4]diazepine-2,12-diamine 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 72.0h， 以71%的产率得到di-tert-butyl 2-(4-(tert-butyl)benzyl)malonate
  参考文献：
  名称：

  Overturning Established Chemoselectivities: Selective Reduction of Arenes over Malonates and Cyanoacetates by Photoactivated Organic Electron Donors

  摘要：

  The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates.

  DOI：

  10.1021/ja4050168
• 作为产物：
  描述：

  丙二酸二叔丁酯 、 4-叔丁基苄溴 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 生成 di-tert-butyl 2,2-bis(4-(tert-butyl)benzyl)malonate
  参考文献：
  名称：

  双光氧化还原/镍催化 β-酮酯和乙烯基叠氮化物的不对称 [3 + 2] 光环加成

  摘要：

  光催化 [3 + 2] 环加成和立体化学的控制仍然是一个巨大的挑战，特别是在杂环合成的背景下；零星的成功例子涉及在含有氧化还原活性直接基团的环丙烷和烯烃之间进行对映选择性 [3 + 2] 光环加成以产生环戊烷。在此，我们报告了一种协同催化系统，该系统包含手性镍路易斯酸催化剂和由可见光照射驱动的有机光催化剂，该系统允许在氧化还原中性条件下实现迄今为止难以实现的 β-酮酯与乙烯基叠氮化物的不对称 [3 + 2] 光环加成状况。该协议能够实现多环密集取代的 3,4-二氢-2 H的高度对映选择性构建-吡咯杂环，具有两个连续的四取代碳立构中心，包括有用的手性N，O-缩酮基序，其他催化方法不易获得。机理研究表明，整体反应性依赖于镍催化剂双重作用的无缝整合，通过催化形成底物/镍络合物，辅助光氧化还原事件和对映选择性自由基加成。

  DOI：

  10.1021/jacs.3c02485

文献信息

• Overturning Established Chemoselectivities: Selective Reduction of Arenes over Malonates and Cyanoacetates by Photoactivated Organic Electron Donors
  作者：Eswararao Doni、Bhaskar Mondal、Steven O’Sullivan、Tell Tuttle、John A. Murphy

  DOI：10.1021/ja4050168

  日期：2013.7.31

  The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates.
• Asymmetric [3 + 2] Photocycloaddition of β-Keto Esters and Vinyl Azides by Dual Photoredox/Nickel Catalysis
  作者：Xue-Song Zhou、Zhihan Zhang、Wen-Yuan Qu、Xiao-Peng Liu、Wen-Jing Xiao、Min Jiang、Jia-Rong Chen

  DOI：10.1021/jacs.3c02485

  日期：2023.6.7

  tetrasubstituted carbon stereocenters, including a useful chiral N,O-ketal motif that is not easily accessible with other catalytic methods. Mechanistic studies revealed that the overall reactivity relies on the seamless integration of dual roles of nickel catalysts by the catalytic formation of the substrate/Ni complex, assisting both photoredox event and enantioselective radical addition.

  光催化 [3 + 2] 环加成和立体化学的控制仍然是一个巨大的挑战，特别是在杂环合成的背景下；零星的成功例子涉及在含有氧化还原活性直接基团的环丙烷和烯烃之间进行对映选择性 [3 + 2] 光环加成以产生环戊烷。在此，我们报告了一种协同催化系统，该系统包含手性镍路易斯酸催化剂和由可见光照射驱动的有机光催化剂，该系统允许在氧化还原中性条件下实现迄今为止难以实现的 β-酮酯与乙烯基叠氮化物的不对称 [3 + 2] 光环加成状况。该协议能够实现多环密集取代的 3,4-二氢-2 H的高度对映选择性构建-吡咯杂环，具有两个连续的四取代碳立构中心，包括有用的手性N，O-缩酮基序，其他催化方法不易获得。机理研究表明，整体反应性依赖于镍催化剂双重作用的无缝整合，通过催化形成底物/镍络合物，辅助光氧化还原事件和对映选择性自由基加成。