2-formyl-2-methyl-1,3-dithiane | 4882-97-7

• 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-formyl-2-methyl-1,3-dithiane
• 英文别名: 2-methyl-1,3-dithiane-2-carbaldehyde；1,3-Dithiane-2-carboxaldehyde, 2-methyl-
• CAS: 4882-97-7
• 化学式: C₆H₁₀OS₂
• 分子量: 162.277
• InChiKey: MPTGKIPTVOWUDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  67.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-formyl-2-methyl-1,3-dithiane 在 4-二甲氨基吡啶 、 bis[(S)-BINOL/Ti(IV)] 、 三乙胺 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 51.5h， 生成
  参考文献：
  名称：

  Asymmetric 1,3-Dipolar Cycloaddition Reaction of Nitrones and Acrolein with a Bis-Titanium Catalyst as Chiral Lewis Acid

  摘要：

  A mu-oxo-type chiral bis-Ti(IV) oxide (S,S)-1 can be successfully utilized in the asymmetric 1,3-dipolar cycloaddition reactions between various nitrones 2 and acrolein to give the corresponding isoxazolidines with high to excellent enantioselectivities. For instance, the reaction between nitrone 2 (R = t-Bu) and acrolein in the presence of 10 mol % of bis-Ti(IV) catalyst (S,S)-1 in dichloromethane at -40 degrees C gave the corresponding endo cycloadduct with 97% ee.

  DOI：

  10.1021/ja0523284
• 作为产物：
  描述：

  bis(2-methyl-1,3-dithian-2-yl)-methanol 在 二苯甲酮 作用下， 以 乙腈 为溶剂， 反应 0.13h， 生成 2-formyl-2-methyl-1,3-dithiane
  参考文献：
  名称：

  含邻位羟基的以硫为中心的阳离子自由基的CC键断裂异常。

  摘要：

  通过氧化光诱导的电子转移产生的在2位具有α-羟基-新戊基或类似基团的1，3-二噻吩基阳离子自由基发生异常断裂，因此需要完善所接受的机理。实验和计算数据支持这样一个理论，即从初始阳离子自由基中的羟基质子抽象出来不会引起Grob样断裂，而是产生一个中性自由基物种，即烷氧基，该烷氧基在任一方向均发生断裂，即裂解CC键与二噻吩基或叔烷基。

  DOI：

  10.1021/jo035001z

文献信息

• Synthesis of 3‐Amino‐4‐iodothiophenes through Iodocyclization of 1‐(1,3‐Dithian‐2‐yl)propargylamines
  作者：Eda Ismailoglu、Zeynep Mert、Mert Dinc、Kerem Kaya、Baris Yucel

  DOI：10.1002/ejoc.202100483

  日期：2021.8.6

  3-Amino-4-iodothiophenes are obtained by iodocyclization of 1,3-dithianyl substituted propargylamine derivatives through iodine induced cleavage of dithiane ring in a bicyclic sulfonium intermediate. 1-(1,3-Dithian-2-yl)propargylamines are readily available by Au-catalyzed reaction of 1,3-dithiane-2-carbaldehydes, amines, and alkynes in a one-pot.

  3-氨基-4-碘噻吩是通过碘代环化1,3-二噻吩基取代炔丙胺衍生物通过碘诱导的双环锍中间体中的二噻烷环裂解获得的。1-(1,3-Dithian-2-yl) 炔丙胺很容易通过 1,3-二噻烷-2-甲醛、胺和炔烃在一锅中的 Au 催化反应获得。
• Exploiting the 1,3-dithiane of 2-oxopropanenitrile oxide to limit competing dimerization in 1,3-dipolar cycloaddition reactions
  作者：Stuart J. Barrow、Christopher J. Easton、G.Paul Savage、Gregory W. Simpson

  DOI：10.1016/s0040-4039(97)00275-x

  日期：1997.3

  The 1,3-dithiane of 2-oxopropanenitrile oxide is less prone to dimerization than the parent compound and, as a consequence, it undergoes more efficient cycloaddition reactions with a range of mono- and 1,1- and 1,2-di-substituted alkenes.

  2-氧代丙烷腈的1,3-二硫杂环丁烷比母体化合物更不容易二聚，因此，它进行更有效的环加成反应，反应范围为单-，1,1-和1,2-二-取代的烯烃。
• Synthetic studies towards spirostaphylotrichins: Synthesis of building blocks
  作者：Olivier Steiner、Christoph Tamm

  DOI：10.1016/s0040-4039(00)61686-6

  日期：1993.10

  A retrosynthetic strategy for the total synthesis of spirostaphylotrichins is presented. The building blocks 7, 8 and 16 were synthesized.

  提出了一种螺旋合成全螺旋螺菌素的逆合成策略。积木7，8和16进行合成。
• Base-Mediated Rearrangement of α-Dithioacetyl Propargylamines via Expansion of Dithioacetyl Ring: Synthesis of Medium-Sized <i>S,S</i>-Heterocycles
  作者：Mert Dinc、Eda Ismailoglu、Zeynep Mert、Kerem Kaya、Melda Tayanc、Baris Yucel

  DOI：10.1021/acs.orglett.3c01118

  日期：2023.6.9

  Base-mediated rearrangement of 1,3-dithianyl-substituted propargylamines in DMF via expansion of the dithiane ring has been reported. The rearrangement provided 9-membered amino-functionalized sulfur-containing heterocycles (dithionine derivatives) in good yields under mild conditions. Propargylamines bearing 5-membered 1,3-dithiolane and 7-membered 1,3-dithiepane rings rearranged in a similar manner

  已经报道了通过二噻烷环的扩展在 DMF 中碱介导的 1,3-二噻吩基取代的炔丙胺重排。该重排在温和条件下以良好的产率提供了 9 元氨基官能化含硫杂环（连二硫氨酸衍生物）。带有 5 元 1,3-二硫杂环戊烷和 7 元 1,3-二噻吩环的丙炔胺以类似的方式重排，分别产生 8 元和 10 元S,S-杂环。
• A Novel [3+2] Cycloaddition Approach to Nitrogen Heterocycles via Phosphine-Catalyzed Reactions of 2,3-Butadienoates or 2-Butynoates and Dimethyl Acetylenedicarboxylate with Imines:  A Convenient Synthesis of Pentabromopseudilin
  作者：Zhenrong Xu、Xiyan Lu

  DOI：10.1021/jo9723063

  日期：1998.7.1

  The reactivity of a new three carbon synthon, generated in situ from the reaction of 2,3-butadienoates or 2-butynoates with an appropriate phosphine as the catalyst, toward the electron deficient imines is described. Triphenylphosphine-catalyzed reaction of-methyl a,3-butadienoate with N-sulfonylimines gave the single [3+2] cycloadduct in excellent yield; tributylphosphine-catalyzed reaction of methyl 2,3-butadienoate or 2-butynoate with N-tosylimines afforded the corresponding [3+2] cycloadduct as the major product along with a small amount of the three components adduct. Aliphatic N-tosylimines gave moderate yield for this reaction. In addition, a new phosphine-catalyzed cyclization reaction of dimethyl acetylenedicarboxylate with N-tosylimines is also described. A:reaction mechanism is proposed. Further elaborations of the cycloaddition products and the synthesis of pentabromopseudilin using this method are exemplified.