meso-3,4-dimethyl-hexa-1,5-diyne-3,4-diol | 4301-16-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: meso-3,4-dimethyl-hexa-1,5-diyne-3,4-diol
• 英文别名: meso/d,l-3,4-dimethyl-1,5-hexadiyne-3,4-diol；rac-3,4-dimethylhexa-1,5-diyne-3,4-diol；racem. 3,4-dimethyl-hexa-1,5-diyne-3,4-diol；DL-3,4-Dimethyl-1,5-hexadiin-3,4-diol
• CAS: 4301-16-0；66415-07-4；66415-08-5
• 化学式: C₈H₁₀O₂
• 分子量: 138.166
• InChiKey: SKLPQBFDKKGMCW-HTQZYQBOSA-N

物化性质

• 沸点：
  76-78 °C(Press: 3 Torr)
• 密度：
  1.121±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.25
• 重原子数：
  10.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  40.46
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4-甲基苯磺酰溴 、 meso-3,4-dimethyl-hexa-1,5-diyne-3,4-diol 以 苯 为溶剂， 反应 2.0h， 以56%的产率得到(1RS,2SR,5E)-dimethyl-3-bromo-5-(toluenesulfonyl-1-ylidenemethyl)cyclopent-3-ene-1,2-diol
  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：

  rac-3,4-dimethyl-1,6-bis(trimethylsilyl)hexa-1,5-diyne-3,4-diol 在 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.0h， 以100%的产率得到meso-3,4-dimethyl-hexa-1,5-diyne-3,4-diol
  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

文献信息

• Rh(I)-katalysierte Umlagerungen von 3,4-Diacycloxy-1,5-hexadiinen; synthese von (<i>E</i>)-4-acyloxymethyliden-2-cyclopenten-1-onen
  作者：Serge Pürro、Andrew Pryde、Janos Zsindely、Hans Schmid

  DOI：10.1002/hlca.19780610124

  日期：1978.1.25

  Rh(I)-Catalysed Rearrangements of 3,4-Diacyloxy-1,5-hexadiynes; Synthesis of (E)-4-Acyloxymethyliden-2-cyclopenten-1-ones

  Rh（I）催化的3,4-二酰氧基-1,5-己二炔的重排; （E）-4-酰氧基亚甲基-2-环戊烯-1-酮的合成
• Synthesis and Structure of Functionalized Cyclododecadiynes and -dienes
  作者：Christoph Boss、Reinhart Keese

  DOI：10.1002/hlca.19960790811

  日期：1996.12.11

  The cyclododecadiynes 3b–d, 8b–d, and 10b–c with functionalities in two propargylic positions, as well as the monofunctionalized diyne 13b have been prepared from simple open-chain building blocks. In the DMPU ( = N,N'-dimethylpropyleneurea)-assisted ring-closing alkylation of 1,7-diynes, the twelve-membered ring compounds have been prepared in yields of 16–55%. The preparation of the diene-diyne 15

  环十二碳二炔3b-d，8b-d和10b-c在两个炔丙基位置具有功能性，以及单官能化的二炔13b已由简单的开链结构单元制备。在DMPU（= N，N'-二甲基丙烯脲）辅助的1,7-二炔的闭环烷基化反应中，制备了十二元环化合物，产率为16-55％。描述了二烯-二炔15和环十二烷基-5,11-二炔-1,4-二酮18的制备。
• 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
  作者：Igor V. Alabugin、Vitaliy I. Timokhin、Jason N. Abrams、Mariappan Manoharan、Rachel Abrams、Ion Ghiviriga

  DOI：10.1021/ja801478n

  日期：2008.8.1

  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.