(3R,1'R,3'R)-3-(1,3-dioxo-1λ4,3λ4-[1,3]dithian-2-yl)-1,3-diphenyl-propan-1-one | 866016-88-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (3R,1'R,3'R)-3-(1,3-dioxo-1λ4,3λ4-[1,3]dithian-2-yl)-1,3-diphenyl-propan-1-one
• 英文别名: (3R,1'R,3'R)-3-(1,3-dioxo-1λ⁴,3λ⁴-[1,3]dithian-2-yl)-1,3-diphenyl-propan-1-one
• CAS: 866016-88-8
• 化学式: C₁₉H₂₀O₃S₂
• 分子量: 360.498
• InChiKey: UJYJVMMHDHKVJL-UOKFIYJESA-N

物化性质

• 熔点：
  80-83 °C(Solv: dichloromethane (75-09-2); hexane (110-54-3))
• 沸点：
  674.1±54.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.27
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  51.21
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (3R,1'R,3'R)-3-(1,3-dioxo-1λ4,3λ4-[1,3]dithian-2-yl)-1,3-diphenyl-propan-1-one 在 [ReOCl₃(PPh₃)₂] 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以90%的产率得到(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 、 过氧化氢异丙苯 、 sodium hexamethyldisilazane 、 (+)-Weinsaeure-diethylester 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.75h， 生成 (3R,1'R,3'R)-3-(1,3-dioxo-1λ4,3λ4-[1,3]dithian-2-yl)-1,3-diphenyl-propan-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

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。