α,α'-phthalimidoyl dibromide | 161092-40-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: α,α'-phthalimidoyl dibromide
• 英文别名: N-(1,3-dibromo-2-oxo-propyl)-phthalimide；N-(1,3-Dibrom-2-oxo-propyl)-phthalimid；2-(1,3-dibromo-2-oxopropyl)-2,3-dihydro-1H-isoindole-1,3-dione；2-(1,3-dibromo-2-oxopropyl)isoindole-1,3-dione
• CAS: 161092-40-6
• 化学式: C₁₁H₇Br₂NO₃
• 分子量: 360.989
• InChiKey: SPXAHCBSIBTVAM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  54.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  α,α'-phthalimidoyl dibromide 在 2,2,2-三氟乙醇 、 氯化铵 、 三乙胺 、 锌 作用下， 以 甲醇 为溶剂， 反应 4.0h， 生成 2β-phthalimidobicyclo<3.2.1>oct-6-en-3-one
  参考文献：
  名称：

  Cycloaddition Reactions of a Nitrogen-Substituted Oxyallyl Cation with Cyclopentadiene and Substituted Furans. Reaction Conditions, Diastereoselectivity, Regioselectivity, and Transition State Modeling

  摘要：

  An investigation of the cycloaddition reactions of a nitrogen-substituted oxyallyl cation is presented. The nitrogen-substituted oxyallyl cation, M(+)-1 (M(+) = H+ or Li+), can be generated from the dibromide 2 using either CF3CH2OH/Et(3)N or LiClO4/CH3CN/Et(3)N. These oxyallyl cations were found to undergo [4 + 2] cycloaddition reactions with furan, cyclopentadiene, 2-methylfuran, and 2-methoxyfuran. The diastereo- and regioselectivities in these reactions were found to be positively influenced by the presence of Li+. Reaction of M(+)-1 with the 2-substituted furans led to primarily those adducts arising from endo addition (as was observed with the unsubstituted dienes) and which had the 2-substituent syn to the bromine. Consideration of the frontier molecular orbitals of the reacting species (Li+-1 and 2-substituted furans calculated at the PM3 semiempirical level of theory) led to the conclusion that FMO theory does not explain the regiochemistry observed in this process, although the relative electrophilicity of M(+)-1 (M(+) = H+ or Li+) could be rationalized. Transition structure modeling was consistent with empirical observations in that it predicted an endo addition of furan to Li+-1 via a stepwise reaction. Calculation of the reaction coordinate for this nonconcerted process predicted a Delta H-rxn similar to -50 kcals/mol and Delta H-act similar to +11 kcal/mol, with the second bond-forming process having a Delta H-act similar to +1.7 kcal/mol.

  DOI：

  10.1021/jo951609z
• 作为产物：
  描述：

  N-丙酮基邻苯二甲酰亚胺 在 溴 作用下， 以 四氯化碳 为溶剂， 以61%的产率得到α,α'-phthalimidoyl dibromide
  参考文献：
  名称：

  The first example of a nitrogen-substituted oxyallyl cation cycloaddition

  摘要：

  The readily available alpha,alpha'-phthalimidoyldibromide 2 has been converted to the first reported N-substituted oxyallyl cation by treatment with either CF3CH2OH or 3MLiClO(4)/Et(2)O in the presence of Et(3)N. The formation of this reactive intermediate has been demonstrated by its in situ cycloaddition with cyclopentadiene and furan.

  DOI：

  10.1016/0040-4039(94)02160-d

文献信息

• A Radical Bidirectional Fragment Coupling Route to Unsymmetrical Ketones
  作者：Lucile Anthore-Dalion、Qiang Liu、Samir Z. Zard

  DOI：10.1021/jacs.6b05344

  日期：2016.7.13

  A powerful strategy for the regioselective bidirectional synthesis of unsymmetrically substituted ketones is described, relying on the fact that the exchange of a xanthate is much faster than the radical addition to an unactivated alkene. The use of an alkene as the formal "alkylating" agent associated with the tolerance for numerous functional groups and the mildness of the experimental conditions

  描述了不对称取代酮的区域选择性双向合成的强大策略，依赖于黄药的交换比未活化烯烃的自由基加成快得多的事实。使用烯烃作为正式的“烷基化”剂，与许多官能团的耐受性和实验条件的温和性相关，消除了与经典离子和过渡金属方法相关的许多问题。
• Gabriel, Chemische Berichte, 1911, vol. 44, p. 1910
  作者：Gabriel

  DOI：——

  日期：——
• The first example of a nitrogen-substituted oxyallyl cation cycloaddition
  作者：Michael A. Walters、Helene R. Arcand、Dawn J. Lawrie

  DOI：10.1016/0040-4039(94)02160-d

  日期：1995.1

  The readily available alpha,alpha'-phthalimidoyldibromide 2 has been converted to the first reported N-substituted oxyallyl cation by treatment with either CF3CH2OH or 3MLiClO(4)/Et(2)O in the presence of Et(3)N. The formation of this reactive intermediate has been demonstrated by its in situ cycloaddition with cyclopentadiene and furan.
• Green; Delaby, Bulletin de la Societe Chimique de France, 1955, p. 704,706
  作者：Green、Delaby

  DOI：——

  日期：——
• Cycloaddition Reactions of a Nitrogen-Substituted Oxyallyl Cation with Cyclopentadiene and Substituted Furans. Reaction Conditions, Diastereoselectivity, Regioselectivity, and Transition State Modeling
  作者：Michael A. Walters、Helene R. Arcand

  DOI：10.1021/jo951609z

  日期：1996.1.1

  An investigation of the cycloaddition reactions of a nitrogen-substituted oxyallyl cation is presented. The nitrogen-substituted oxyallyl cation, M(+)-1 (M(+) = H+ or Li+), can be generated from the dibromide 2 using either CF3CH2OH/Et(3)N or LiClO4/CH3CN/Et(3)N. These oxyallyl cations were found to undergo [4 + 2] cycloaddition reactions with furan, cyclopentadiene, 2-methylfuran, and 2-methoxyfuran. The diastereo- and regioselectivities in these reactions were found to be positively influenced by the presence of Li+. Reaction of M(+)-1 with the 2-substituted furans led to primarily those adducts arising from endo addition (as was observed with the unsubstituted dienes) and which had the 2-substituent syn to the bromine. Consideration of the frontier molecular orbitals of the reacting species (Li+-1 and 2-substituted furans calculated at the PM3 semiempirical level of theory) led to the conclusion that FMO theory does not explain the regiochemistry observed in this process, although the relative electrophilicity of M(+)-1 (M(+) = H+ or Li+) could be rationalized. Transition structure modeling was consistent with empirical observations in that it predicted an endo addition of furan to Li+-1 via a stepwise reaction. Calculation of the reaction coordinate for this nonconcerted process predicted a Delta H-rxn similar to -50 kcals/mol and Delta H-act similar to +11 kcal/mol, with the second bond-forming process having a Delta H-act similar to +1.7 kcal/mol.