(1R,3R)-2-pentylidene-1λ⁴,3λ⁴-dithiane-1,3-dioxide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: (1R,3R)-2-pentylidene-1λ⁴,3λ⁴-dithiane-1,3-dioxide
• 英文别名: (1R,3R)-2-pentylidene-1,3-dithiane 1,3-dioxide
• 化学式: C₉H₁₆O₂S₂
• 分子量: 220.357
• InChiKey: KOBXQPOEPXABAQ-CHWSQXEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  72.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-pentylidene-1,3-dithiane 在 titanium(IV) isopropylate 、 过氧化氢异丙苯 、 (+)-Weinsaeure-diethylester 作用下， 以 二氯甲烷 为溶剂， 以76%的产率得到(1R,3R)-2-pentylidene-1λ⁴,3λ⁴-dithiane-1,3-dioxide
  参考文献：
  名称：

  Enolate Addition to a 2-Alkylidene[1,3]dithiane-Derived Bissulfoxide. A New a²-Acceptor

  摘要：

  Reaction of enolates derived from esters and ketones to an easily prepared alkylidene[1,3]dithiane-1,3-dioxide afforded the respective adducts with good yields and selectivities generally exceeding 85:15. The base used for enolate addition played no significant role for the reaction outcome, and addition of a silyl enole ether gave similar results. The thus formed oxygenated S,S-acetals were transformed into the corresponding 1,4-dicarbonyls by a reduction/oxidation sequence with 84% yield.

  DOI：

  10.1021/ol051670i

文献信息

• Additions of aldehydes to metallated trans-1,3-Dithiane-S,S-dioxide under conditions of kinetic and thermodynamic control
  作者：Varinder K Aggarwal、Ian W Davies、John Maddock、Mary F Mahon、Kieran C Molloy

  DOI：10.1016/s0040-4039(00)94354-5

  日期：1990.1

  The chiral acyl anion equivalent (1) can be metallated with n-BuLi/py and reacts with aldehydes to give adducts in high yield. At −78δC the reaction is under kinetic control whereas at 0δC equilibration occurs with PhCHO and t-BuCHO resulting in good yields of single diastereoisomers.

  手性酰基阴离子当量（1）可以用n-BuLi / py进行金属化，并与醛反应以高收率得到加合物。在-78δC时，反应处于动力学控制之下，而在0δC时，PhCHO和t-BuCHO发生平衡，从而导致单一非对映异构体的收率很高。
• Highly Enantioselective Oxidations of Ketene Dithioacetals Leading to Trans Bis-sulfoxides
  作者：Varinder K. Aggarwal、Rebecca M. Steele、Ritmaleni、Juliet K. Barrell、Ian Grayson

  DOI：10.1021/jo034032r

  日期：2003.5.1

  Sharpless-type asymmetric oxidation using (+)-DET, Ti(O(i)()Pr)(4), and cumene hydroperoxide to give the trans bis-sulfoxides 4a-f with essentially complete control of enantioselectivity and diastereoselectivity. The high enantioselectivity is a consequence of carrying out two asymmetric processes on the same substrate. However, this should lead to the formation of a small amount of the meso isomer but none was

  乙炔二硫缩醛使用（+）-DET，Ti（O（i）（）Pr）（4）和氢过氧化枯烯进行Sharpless型不对称氧化，得到反双亚砜4a-f，基本上控制了对映选择性和非对映选择性。高对映选择性是在同一基质上进行两个不对称过程的结果。但是，这应导致形成少量的内消旋异构体，但没有一个被分离出来。通过监测随时间的一氧化碳的对映选择性，可以得出结论，必须形成少量的内消旋异构体。无法分离该化合物可能是因为它充当钛上的配体并且即使在后处理时也保持紧密结合。
• Anion Reactions of 1,3-Dithiane 1,3-Dioxide with Carbonyl Compounds: High Diastereoselectivity with Aromatic Aldehydes under Conditions of Equilibrium Control
  作者：Varinder K. Aggarwal、Richard Franklin、John Maddock、Graham R. Evans、Abraham Thomas、Mary F. Mahon、Kieran C. Molloy、Martin J. Rice

  DOI：10.1021/jo00112a042

  日期：1995.4

  We have investigated the anion chemistry of trans-1,3-dithiane 1,3-dioxide (4) with aldehydes and ketones, and we have found that this reagent undergoes highly selective addition reactions with aromatic aldehydes but only when reactions are under equilibrium control (achieved using Na anion of 4). Other metals invetsigated (Li, Mg, Al, Ce, Ti) gave either poorer selectivity or caused decomposition of 4. Zn-4 did give improved selectivity at low temperature but only with aromatic aldehydes. Reactions with ketones were limited to those without a-branching. A model that accounts for the high diastereoselectivity observed with aromatic aldehydes is presented.
• AGGARWAL, VARINDER K.;DAVIES, IAN W.;MADDOCK, JOHN;MAHON, MARY F.;MOLLOY,+, TETRAHEDRON LETT., 31,(1990) N, C. 135-138
  作者：AGGARWAL, VARINDER K.、DAVIES, IAN W.、MADDOCK, JOHN、MAHON, MARY F.、MOLLOY,+

  DOI：——

  日期：——
• Enolate Addition to a 2-Alkylidene[1,3]dithiane-Derived Bissulfoxide. A New a²-Acceptor
  作者：Tobias Wedel、Joachim Podlech

  DOI：10.1021/ol051670i

  日期：2005.9.1

  Reaction of enolates derived from esters and ketones to an easily prepared alkylidene[1,3]dithiane-1,3-dioxide afforded the respective adducts with good yields and selectivities generally exceeding 85:15. The base used for enolate addition played no significant role for the reaction outcome, and addition of a silyl enole ether gave similar results. The thus formed oxygenated S,S-acetals were transformed into the corresponding 1,4-dicarbonyls by a reduction/oxidation sequence with 84% yield.