2-hex-1-ynyl-2-isopropyl-1,3-dithiolane | 253436-82-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: 2-hex-1-ynyl-2-isopropyl-1,3-dithiolane
• 英文别名: 2-Hex-1-ynyl-2-propan-2-yl-1,3-dithiolane
• CAS: 253436-82-7
• 化学式: C₁₂H₂₀S₂
• 分子量: 228.423
• InChiKey: MGFCYGQMFXLSJY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-hex-1-ynyl-2-isopropyl-1,3-dithiolane 在 甲基碘化镁 、 iron(III)-acetylacetonate 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 甲苯 为溶剂， 反应 1.0h， 生成 3-methyl-4-isopropyl-1-trimethylsilyldec-3E-en-1,5-diyne
  参考文献：
  名称：

  Iron-Promoted Elimination of β-Thioalkoxy Alcohols. Olefination by Coupling of a Carbonyl Group with a Dithioacetal

  摘要：

  Treatment of propargylic dithiolanes with (BuLi)-Bu-n followed by a carbonyl electrophile yields the corresponding propargylic dithioacetals. Upon treatment with 1 equiv of Fe(acac)(3) and excess MeMgI, elimination of SR and OH moieties from 8 affords the corresponding olefins in satisfactory yield. Benzylic dithioacetals behave similarly. The reaction can be considered an alternative of McMurry coupling of two different carbonyl equivalents.

  DOI：

  10.1021/ol701579f
• 作为产物：
  描述：

  (2-isopropyl-1,3-dithiolan-2-ylethynyl)-trimethylsilane 在 正丁基锂 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 0.5h， 生成 2-hex-1-ynyl-2-isopropyl-1,3-dithiolane
  参考文献：
  名称：

  Iron-Promoted Elimination of β-Thioalkoxy Alcohols. Olefination by Coupling of a Carbonyl Group with a Dithioacetal

  摘要：

  Treatment of propargylic dithiolanes with (BuLi)-Bu-n followed by a carbonyl electrophile yields the corresponding propargylic dithioacetals. Upon treatment with 1 equiv of Fe(acac)(3) and excess MeMgI, elimination of SR and OH moieties from 8 affords the corresponding olefins in satisfactory yield. Benzylic dithioacetals behave similarly. The reaction can be considered an alternative of McMurry coupling of two different carbonyl equivalents.

  DOI：

  10.1021/ol701579f

文献信息

• Elimination of β-Thioalkoxy Alcohols under Mitsunobu Conditions. A New Synthesis of Conjugated Enynes from Propargylic Dithioacetals
  作者：Chih-Wei Chen、Tien-Yau Luh

  DOI：10.1021/jo8013885

  日期：2008.11.7

  Treatment of propargylic dithiolanes 1 with (n)BuLi followed by a carbonyl electrophile yields the corresponding homopropargylic alcohol 3. Upon treatment with 2 equiv of PPh3 and DIAD, elimination of SR and OH moieties from 3 affords the corresponding olefins 4 in moderate to good yield. The reaction can be considered an alternative of McMurry coupling of two different carbonyl equivalents.

  用（n）BuLi然后用羰基亲电试剂处理炔丙基二硫杂环戊烷1得到相应的均炔丙基醇3。用2当量的PPh3和DIAD处理后，从3中除去SR和OH部分得到相应的烯烃4，产率中等至良好。该反应可以被认为是两种不同的羰基当量的麦克默里偶联的替代方法。
• Umpolung of Carbon−Sulfur Bonds. Novel Synthesis of Substituted Allenes from Propargylic Dithioacetals
  作者：Hsian-Rong Tseng、Chin-Fa Lee、Lian-Ming Yang、Tien-Yau Luh

  DOI：10.1021/jo991032b

  日期：1999.11.1

  Umpolung of the carbon-sulfur bonds can be achieved by treatment of propargylic dithioacetals 1 with organocuprates. The organocopper intermediates 3 gave the corresponding allenyl thioethers 4 upon protonolysis. When alkyl halides were used, propargylic thioethers 5 were obtained exclusively. Transmetalation of organocopper intermediates 3 with ZnBr2 followed by Pd(PPh3)(4)- catalyzed coupling with vinylic or aryl halides afforded the corresponding allenyl thioethers 4. Either 4 or 5 reacted with Grignard reagents in the presence of NiCl2(dppf) to yield the corresponding allenes 9 or 10, respectively. The overall reaction can be considered to use 1 as allene-1,3-zwitterion synthons. The relative reactivities of a propargylic ether versus a propargylic dithioacetal toward an organocopper reagent were compared. The sulfur moiety apparently has higher reactivity toward the copper reagent.
• Mercuric acetate-mediated annulation of homopropargylic alcohols having thioether substituent. A general route for the synthesis of tetrasubstituted furans from propargylic dithioacetals
  作者：Chih-Wei Chen、Tien-Yau Luh

  DOI：10.1016/j.tetlet.2009.02.043

  日期：2009.7

  Treatment of an alkyl-substituted propargylic dithioacetal with (BuLi)-Bu-n followed by an aldehyde furnishes thio-substituted homopropargylic alcohol 7 which undergoes annulation in the presence of two equivalents of mercury acetate to give the corresponding mercurio-substituted furan 12. Reaction of 12 with iodine gives iodofuran in moderate to good yield. (C) 2009 Elsevier Ltd. All rights reserved.