(1R,3R)-2-phenylmethylidene-1λ⁴,3λ⁴-dithiane-1,3-dioxide | 214899-59-9

• 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-phenylmethylidene-1λ⁴,3λ⁴-dithiane-1,3-dioxide
• 英文别名: (1R,3R)-2-benzylidene-1λ⁴,3λ⁴-dithiane-1,3-dioxide；(R_S,R_S)-2-benzylidene-1,3-dithiane-1,3-dioxide；(1R,3R)-2-benzylidene-1,3-dithiane 1,3-dioxide
• CAS: 214899-59-9
• 化学式: C₁₁H₁₂O₂S₂
• 分子量: 240.347
• InChiKey: USQWJAIJRBVYFU-HUUCEWRRSA-N

物化性质

• 熔点：
  174-175 °C(Solv: dichloromethane (75-09-2); hexane (110-54-3))
• 沸点：
  573.6±50.0 °C(Predicted)
• 密度：
  1.43±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  72.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,3R)-2-phenylmethylidene-1λ⁴,3λ⁴-dithiane-1,3-dioxide 在 [ReOCl₃(PPh₃)₂] 、 四丁基氟化铵 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 (R)-3-([1,3]dithian-2-yl)-1,3-diphenylpropan-1-one
  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
• 作为产物：
  描述：

  2-benzylidene-1,3-dithiane 在 titanium(IV) isopropylate 、 (+)-Weinsaeure-diethylester 、 过氧化氢异丙苯 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以73%的产率得到(1R,3R)-2-phenylmethylidene-1λ⁴,3λ⁴-dithiane-1,3-dioxide
  参考文献：
  名称：

  烯酮二硫缩醛的高度对映选择性氧化，导致反式双亚砜。

  摘要：

  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。

  DOI：

  10.1021/jo034032r

文献信息

• Nucleophilic Additions to Alkylidene Bis(sulfoxides)—Stereoelectronic Effects in Vinyl Sulfoxides
  作者：Tobias Wedel、Timo Gehring、Joachim Podlech、Elena Kordel、Angela Bihlmeier、Wim Klopper

  DOI：10.1002/chem.200701847

  日期：2008.5.19

  Conjugate additions of nucleophiles (e.g. enolates, amines and malonate anions) to bis(p-tolylsulfinyl)alkenes, alkylidene-1,3-dithiane-1,3-dioxides and alkylidene-1,3-dithiolane-1,3-dioxides have recently been published. Reasons for different selectivities and reaction rates will be discussed by consideration of steric and electronic effects. The preferred mode of attack can be explained by stereoelectronic

  将亲核试剂（例如，烯酸酯，胺和丙二酸根阴离子）共轭添加到双（对甲苯基亚磺酰基）烯烃，亚烷基-1,3-二硫代-1,3-二氧化物和亚烷基-1,3-二硫代-1,3-二氧化物中最近已出版。将通过考虑空间效应和电子效应来讨论选择性和反应速率不同的原因。首选的攻击方式可以通过主要碳负离子中的立体电子效应（超共轭）来解释，该作用通过n-> SO-sigma *与反周平面S = O基团的相互作用来稳定。将丙酮烯酸酯添加至二噻烷衍生的亚烷基双（亚砜）的过渡态[BP86 / aug-TZVP]的计算表明，攻击所需的能量更多，为6.6-7.3 kJ mol（-1），从而减少了稳定的碳负离子。
• 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。
• Stereoselective Epoxidation of bis-Sulfinyl Alkenes and Application to the Asymmetric Synthesis of α-Substituted Carboxylic Acids
  作者：Varinder K. Aggarwal、Julia M. Worrall、Rikki Alexander

  DOI：10.1080/10426509708545544

  日期：1997.1.1

  thioacetals 3 can be easily prepared in optically pure form and react diastereoselectively with metal peroxides. The resulting bis-sulfinyl oxiranes can be converted in a single step to α-substituted acids.

  乙烯酮硫缩醛 3 可以很容易地以光学纯形式制备，并与金属过氧化物进行非对映选择性反应。生成的双亚磺酰基环氧乙烷可以在一步中转化为 α-取代的酸。
• Stereoelectronic Effects in Cyclic Sulfoxides, Sulfones, and Sulfilimines: Application of the Perlin Effect to Conformational Analysis
  作者：Tobias Wedel、Monika Müller、Joachim Podlech、Helmut Goesmann、Claus Feldmann

  DOI：10.1002/chem.200601468

  日期：2007.5.18

  The 1JC--H coupling constants in conformationally constrained sulfoxides, bissulfoxides, sulfoxide-sulfones, and sulfilimines derived from 2-benzylidene-1,3-dithiane and 2-(2,2-dimethylpropylidene)-1,3-dithiolane were measured by means of HMQC and HSQC NMR experiments and the Perlin effects were calculated. The type and the relative configuration of S==X groups (X= O, NTos) in these compounds have

  构象受限的亚砜，双亚砜，亚砜砜和由2-苄叉基-1,3-二噻吩和2-（2,2-二甲基丙叉基）-1,3-二硫杂环戊烷衍生的亚砜亚胺中的1JC-H耦合常数通过用HMQC和HSQC NMR实验的平均值和Perlin效应进行计算。这些化合物中S == X（X = O，NTos）的类型和相对构型分别对轴向键和赤道CH键的偶联常数的大小有很大影响。轴向S == O键对反平面的轴向C-H键产生立体电子效应。与相应的赤道CH键相比，相应的CH键的弱化导致较小的偶合常数。赤道S == O基团通过同分异构效应对β-C-H键产生影响。这里，轴向C–H键被削弱，并且测得的耦合常数更小。亚磺胺基团显示出与亚砜基团相似的作用。
• 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.