meso-2,3-diethynyl-2,3-dimethyl[1,4]dioxane | 1039753-10-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: meso-2,3-diethynyl-2,3-dimethyl[1,4]dioxane
• 英文别名: Me2(HCC)2C4H4O2；(2S,3R)-2,3-diethynyl-2,3-dimethyl-1,4-dioxane
• CAS: 1039753-10-0
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: JHRLYHIKDWGJRS-AOOOYVTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  meso-2,3-diethynyl-2,3-dimethyl[1,4]dioxane 在 偶氮二异丁腈 、 三正丁基氢锡 、 三氟乙酸 作用下， 以 苯 、 氘代氯仿 为溶剂， 反应 21.0h， 生成 (4aSR,7aRS)-5-ylidenemethyl-2,3-dihydrocyclopenta[1,4]dioxin
  参考文献：
  名称：

  In Search of Efficient 5-Endo-dig Cyclization of a Carbon-Centered Radical: 40 Years from a Prediction to Another Success for the Baldwin Rules

  摘要：

  Despite being predicted to be stereoelectronically favorable by the Baldwin rules, efficient formation of a C-C bond through a 5-endo-dig radical cyclization remained unknown for more than 40 years. This work reports a remarkable increase in the efficiency of this process upon beta-Ts substitution, which led to the development of an expedient approach to densely functionalized cyclic 1,3-dienes. Good qualitative agreement between the increased efficiency and stereoselectivity for the 5-endo-dig cyclization of Ts-substituted vinyl radicals and the results of density functional theory analysis further confirms the utility of computational methods in the design of new radical processes. Although reactions of Br atoms generated through photochemical Ts-Br bond homolysis lead to the formation of cyclic dibromide side products, the yields of target bromosulfones in the photochemically induced reactions can be increased by recycling the dibromide byproduct into the target bromosulfones through a sequence of addition/elimination reactions at the exocyclic double bond. Discovery of a relatively efficient radical 5-endo-dig closure, accompanied by a C-C bond formation, provides further support to stereoelectronic considerations at the heart of the Baldwin rules and fills one of the last remaining gaps in the arsenal of radical cyclizations.

  DOI：

  10.1021/ja801478n
• 作为产物：
  描述：

  meso-3,4-dimethyl-1,6-bis(trimethylsilyl)hexa-1,5-diyne-3,4-diol 、 1,2-二氯乙烷 在 sodium hydroxide 、 四丁基氟化铵 作用下， 以 水 为溶剂， 反应 64.0h， 以47%的产率得到meso-2,3-diethynyl-2,3-dimethyl[1,4]dioxane
  参考文献：
  名称：

  In Search of Efficient 5-Endo-dig Cyclization of a Carbon-Centered Radical: 40 Years from a Prediction to Another Success for the Baldwin Rules

  摘要：

  Despite being predicted to be stereoelectronically favorable by the Baldwin rules, efficient formation of a C-C bond through a 5-endo-dig radical cyclization remained unknown for more than 40 years. This work reports a remarkable increase in the efficiency of this process upon beta-Ts substitution, which led to the development of an expedient approach to densely functionalized cyclic 1,3-dienes. Good qualitative agreement between the increased efficiency and stereoselectivity for the 5-endo-dig cyclization of Ts-substituted vinyl radicals and the results of density functional theory analysis further confirms the utility of computational methods in the design of new radical processes. Although reactions of Br atoms generated through photochemical Ts-Br bond homolysis lead to the formation of cyclic dibromide side products, the yields of target bromosulfones in the photochemically induced reactions can be increased by recycling the dibromide byproduct into the target bromosulfones through a sequence of addition/elimination reactions at the exocyclic double bond. Discovery of a relatively efficient radical 5-endo-dig closure, accompanied by a C-C bond formation, provides further support to stereoelectronic considerations at the heart of the Baldwin rules and fills one of the last remaining gaps in the arsenal of radical cyclizations.

  DOI：

  10.1021/ja801478n