(+)-(R)-1,3-diphenyl-3-phenylsulfonylpropan-1-one | 500296-16-2

• 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: (+)-(R)-1,3-diphenyl-3-phenylsulfonylpropan-1-one
• 英文别名: (R)-1,3-diphenyl-3-(phenylsulfonyl)propan-1-one；(3R)-3-(benzenesulfonyl)-1,3-diphenylpropan-1-one
• CAS: 500296-16-2
• 化学式: C₂₁H₁₈O₃S
• 分子量: 350.438
• InChiKey: BSLYDZFKDICYCT-OAQYLSRUSA-N

物化性质

• 沸点：
  571.4±50.0 °C(Predicted)
• 密度：
  1.229±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  59.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-(R)-1,3-diphenyl-3-phenylsulfonylpropan-1-one 在 lithium aluminium tetrahydride 、 18-冠醚-6 、 potassium tert-butylate 、 三乙胺 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 11.0h， 生成 (-)-(1R,2R)-1,2-diphenyl-1-phenylsulfonylcyclopropane
  参考文献：
  名称：

  A new and efficient route to homochiral γ-hydroxysulfoxides and γ-hydroxysulfones

  摘要：

  Readily available (+)- (R)-1,3-diphenyl-3-phenylsulfanyl-propan-1-one 1 was oxidized to the corresponding sulfone and its reduction gave separable (1R,3R)- and (1S,3R)-1,3-diphenyl-3-phenylsulfonylpropan-1-ols. When I was reduced to the mixture of epimeric alcohols, subsequent reaction with three different sulfoxidation agents allowed the separation of all four diastereomeric, 1,3-diphenyl-3-phenylsulfinylpropan-1-ols in diastereomerically pure form. The absolute configuration at the newly created stereogenic carbon was proved by chemical correlation, while the configuration of the sulfur centre of the phenylsulfinyl group was established by CD spectroscopy. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00581-5
• 作为产物：
  描述：

  苯亚甲基苯乙酮 在 potassium fluoride 、 C₄₆H₅₀I₄O₆ 作用下， 以 1,4-二氧六环 、 甲苯 为溶剂， 反应 60.0h， 生成 (+)-(R)-1,3-diphenyl-3-phenylsulfonylpropan-1-one
  参考文献：
  名称：

  阳离子结合聚醚催化剂通过对映选择性消除β-磺酰基酮的动力学拆分

  摘要：

  本文报道的是手性阳离子结合聚醚催化的第一个对映选择性β-消除反应。通过使用这种催化方案，可以以高的立体选择性（S高达> 300）有效地分离各种β-磺酰基酮。该方法成功的关键是催化剂与砜基质上的路易斯碱性基团之间有利的二次相互作用。该方法的烯酮产物可轻松转化为外消旋原料，并可以高收率和出色的对映选择性有效地循环利用和全面合成手性β-磺酰基酮。

  DOI：

  10.1002/anie.201508127

文献信息

• [EN] A METHOD FOR PREPARING SULFUR-CONTAINING COMPOUNDS<br/>[FR] PROCÉDÉ POUR LA PRÉPARATION DE COMPOSÉS CONTENANT DU SOUFRE
  申请人：ROYAL COLLEGE OF SURGEONS IE

  公开号：WO2010066450A1

  公开（公告）日：2010-06-17

  The invention provides a method for preparing sulfur-containing compounds, the method comprising reacting a donor compound comprising at least one sulfur having at least one lone pair of electrons, with an acceptor compound; wherein the reaction occurs in the presence of an amine, optionally an amine catalyst, capable of activating the sulfur having at least one lone pair of electrons; and wherein the reaction occurs via the formation of an transient intermediate species, optionally a transient intermediate species, between the amine, optionally the amine catalyst and the donor compound; and wherein the donor compound is selected from the group consisting of a sulfurous acid, a sulfenic acid and a sulfinic acid or a salt, ester or amide of a sulfurous acid, a sulfenic acid and a sulfinic acid. The invention also provides sulfur-containing compounds of the formula: wherein R is selected from: (a) 1 -(4-Nitro-phenyl)-3-oxo-3-phenyl-propane; (b) 2-(3-Methyl-4-nitro-isoxazol-5-yl)-1 -phenyl-ethane; (c) 1-(4-Methoxy-phenyl)-2-(3-methyl-4-nitro-isoxazol-5-yl)-ethane; (d) 2-(3-Methyl-4-nitro-isoxazol-5-yl)-1-(4-nitro-phenyl)-ethane; (e) 1-(4-Fluoro-phenyl)-2-(3-methyl-4-nitro-isoxazol-5-yl)-ethane; (f) 1 -(4-Chloro-phenyl)-2-(3-methyl-4-nitro-isoxazol-5-yl)-ethane; and (g) 3-Oxo-cyclohexane. Finally, the invention provides use of chiral sulfur-containing compounds obtainable by the above-mentioned method or chiral sulfur-containing compounds as mentioned above for the resolution of racemic mixtures of amines.

  该发明提供了一种制备含硫化合物的方法，该方法包括将包含至少一个硫原子且至少一个孤对电子的给体化合物与受体化合物反应；其中，在胺的存在下进行反应，可选地，在能够激活至少一个硫原子具有至少一个孤对电子的胺的存在下进行反应；反应通过形成瞬态中间体物种进行，可选地，通过胺、可选地胺催化剂和给体化合物之间的瞬态中间体物种进行反应；给体化合物选自包括亚硫酸、亚硫酸和亚砜酸或亚硫酸、亚硫酸和亚砜酸的盐、酯或酰胺的群；该发明还提供了符合以下公式的含硫化合物：其中R选自：(a) 1-(4-硝基苯基)-3-氧代-3-苯基-丙烷；(b) 2-(3-甲基-4-硝基异噁唑-5-基)-1-苯基-乙烷；(c) 1-(4-甲氧基苯基)-2-(3-甲基-4-硝基异噁唑-5-基)-乙烷；(d) 2-(3-甲基-4-硝基异噁唑-5-基)-1-(4-硝基苯基)-乙烷；(e) 1-(4-氟苯基)-2-(3-甲基-4-硝基异噁唑-5-基)-乙烷；(f) 1-(4-氯苯基)-2-(3-甲基-4-硝基异噁唑-5-基)-乙烷；和(g) 3-氧代环己烷。最后，该发明提供了通过上述方法获得的手性含硫化合物或上述提到的手性含硫化合物用于分离胺的外消旋混合物。
• Enantioselective Sulfonation of Enones with Sulfinates by Thiourea/Tertiary-Amine Catalysis
  作者：Guang-xun Li、Jin-zhong Zhao、Si-fan Wang、Ming Yan、Jin-yi Shi

  DOI：10.1055/a-2202-0842

  日期：——

  substrates that could be converted into sulfinic acids by treatment with boric acid. The bifunctional catalyst forms a chiral ion pair with the sulfinic acid and controls the enantioselectivity of the sulfonation through hydrogen bonding.

  手性γ-酮砜是有机合成和药物化学中的重要结构。尽管获得外消旋形式有多种选择，但仅报道了少数对映选择性方法。我们开发了一种简单的方法，可以以中等产率和中等对映体比例获得手性 γ-酮砜。直接使用现成的亚磺酸盐作为底物，通过硼酸处理可以将其转化为亚磺酸。双功能催化剂与亚磺酸形成手性离子对，并通过氢键控制磺化的对映选择性。
• Kinetic Resolution of β-Sulfonyl Ketones through Enantioselective β-Elimination using a Cation-Binding Polyether Catalyst
  作者：Liang Li、Yidong Liu、Yang Peng、Lei Yu、Xiaoyan Wu、Hailong Yan

  DOI：10.1002/anie.201508127

  日期：2016.1.4

  Reported herein is the first enantioselective β‐elimination reaction catalyzed by a chiral cation‐binding polyether. By using this catalytic protocol, a wide range of β‐sulfonyl ketones could be effectively resolved with high stereoselectivity (S up to >300). Key to the success of this process is the favorable secondary interactions of the catalyst with the Lewis basic groups on the sulfone substrate

  本文报道的是手性阳离子结合聚醚催化的第一个对映选择性β-消除反应。通过使用这种催化方案，可以以高的立体选择性（S高达> 300）有效地分离各种β-磺酰基酮。该方法成功的关键是催化剂与砜基质上的路易斯碱性基团之间有利的二次相互作用。该方法的烯酮产物可轻松转化为外消旋原料，并可以高收率和出色的对映选择性有效地循环利用和全面合成手性β-磺酰基酮。
• A new and efficient route to homochiral γ-hydroxysulfoxides and γ-hydroxysulfones
  作者：Jacek Skarżewski、Renata Siedlecka、Elżbieta Wojaczyńska、Mariola Zielińska-Błajet

  DOI：10.1016/s0957-4166(02)00581-5

  日期：2002.10

  Readily available (+)- (R)-1,3-diphenyl-3-phenylsulfanyl-propan-1-one 1 was oxidized to the corresponding sulfone and its reduction gave separable (1R,3R)- and (1S,3R)-1,3-diphenyl-3-phenylsulfonylpropan-1-ols. When I was reduced to the mixture of epimeric alcohols, subsequent reaction with three different sulfoxidation agents allowed the separation of all four diastereomeric, 1,3-diphenyl-3-phenylsulfinylpropan-1-ols in diastereomerically pure form. The absolute configuration at the newly created stereogenic carbon was proved by chemical correlation, while the configuration of the sulfur centre of the phenylsulfinyl group was established by CD spectroscopy. (C) 2002 Elsevier Science Ltd. All rights reserved.