(S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde | 794525-98-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde
• 英文别名: Benzeneacetaldehyde, 2-[(S)-(4-methylphenyl)sulfinyl]-；2-[2-[(S)-(4-methylphenyl)sulfinyl]phenyl]acetaldehyde
• CAS: 794525-98-7
• 化学式: C₁₅H₁₄O₂S
• 分子量: 258.341
• InChiKey: BSERVJJSENUZQO-SFHVURJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  53.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde 在 4 A molecular sieve 、 镍 、 ytterbium(III) triflate 作用下， 以 乙醇 、 乙腈 为溶剂， 反应 5.08h， 生成 (2R,4R)-2-benzyltetrahydro-2H-pyran-4-ol
  参考文献：
  名称：

  Efficient trans-Selectivity in the Cyclocondensation of (S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde with Activated Dienes Catalyzed by Yb(OTf)₃

  摘要：

  Reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde 1 with Danishefsky's and related dienes took place in the presence of Yb(OTf)(3) in a completely stereoselective manner, mediated by a remote sulfinyl group (1,5-asymmetric induction), to afford the corresponding 2,3-dihydro-4H-pyran-4-ones. These reactions followed a stepwise mechanism, as was corroborated by isolation of the corresponding intermediates, with a high level of trans-selectivity for 4-methyl-substituted dienes. Treatment of the adducts with Raney Ni provided concomitant cleavage of the C-S bond and reduction of the conjugated carbonyl grouping.

  DOI：

  10.1021/jo061128n
• 作为产物：
  描述：

  (S)-1-(2,2-dimethoxyethyl)-2-(p-tolylsulfinyl)benzene 在 甲酸 作用下， 反应 1.0h， 以99%的产率得到(S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde
  参考文献：
  名称：

  手性邻-（对甲苯磺酰基）苄基酮的合成

  摘要：

  通过酯或腈与衍生自2-（对甲苯基亚磺酰基）甲基苯的苄基碳负离子的反应，可以高收率制备（S）-邻-（对甲苯基亚磺酰基）苄基烷基（和芳基）酮1a - e。制备α-甲基苄基酮2。通过用NaH / MeI甲基化未取代的酮1形成1：1的非对映异构体混合物。使用乙苯衍生物作为起始原料得到复杂的混合物。纯（S，（S）S）-2的遵守非对映异构体可以通过用PCC氧化由醛与衍生自2-（对甲苯基亚磺酰基）乙苯的锂碳负离子反应得到的醇（羟基碳上的异构体混合物）而以高收率获得。

  DOI：

  10.1016/j.tet.2004.07.050

文献信息

• The Sulfinyl Group as a Remote Chiral Auxiliary in Stereoselective Conjugate Additions of Alkyl Groups to α-Methylidene Carbonyl Compounds Initiated by Et₃B/O₂
  作者：José Antonio Fernández-Salas、M. Carmen Maestro、M. Mercedes Rodríguez-Fernández、José L. García Ruano

  DOI：10.1002/ejoc.201201642

  日期：2013.3

  l] α-methylidene carbonyl compounds 1 and 2 with alkyl radicals generated from Et3B/O2 and RI give, after protonation, β-alkyl derivatives with a high degree of control of the configuration at the α carbon. In the case of aldehyde 2, when further combined with allylation of the carbonyl group, a one-pot radical-addition/protonation/allylation sequence provides a highly stereoselective synthesis of

  α-[2-(对甲苯基亚磺酰基)苯基] α-亚甲基羰基化合物 1 和 2 与由 Et3B/O2 和 RI 产生的烷基反应，在质子化后得到具有高度可控构型的 β-烷基衍生物在α碳。在醛 2 的情况下，当进一步与羰基的烯丙基化结合时，一锅自由基加成/质子化/烯丙基化序列提供了具有两个相邻手性中心的化合物的高度立体选择性合成。反应的立体化学过程由作为远程手性助剂的亚磺酰基控制，该基团可以很容易地用 tBuLi 去除。
• Remote stereocontrol by the sulfinyl group: Mukaiyama aldol reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde in the asymmetric synthesis of β-hydroxyacids and 1,3-diols
  作者：José L. García Ruano、M. Ángeles Fernández-Ibáñez、M. Carmen Maestro

  DOI：10.1016/j.tet.2006.10.010

  日期：2006.12

  (S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde reacts with different O-silylated ketenethioacetals in the presence of Yb(OTf)3 yielding β-hydroxythioesters in high yields and diastereoselectivities. The obtained compounds were readily transformed into β-hydroxyacids and their corresponding diols. These Mukaiyama aldol reactions are a direct evidence of the ability of the sulfinyl group to control 1

  （S）-2- [2-（对甲苯磺酰基）苯基]乙醛在Yb（OTf）3存在下与不同的O-甲硅烷基化的酮硫缩醛反应，以高产率和非对映选择性生成β-羟基硫酯。所获得的化合物易于转化为β-羟基酸及其相应的二醇。这些Mukaiyama羟醛反应是亚磺酰基控制1,5-和1,6-不对称诱导过程的能力的直接证据。
• Remote stereocontrol by sulfinyl groups: hydrocyanation of δ-ketosulfoxides
  作者：José L. García Ruano、M. Ángeles Fernández-Ibáñez、M. Carmen Maestro、M. Mercedes Rodríguez-Fernández

  DOI：10.1016/j.tet.2005.10.067

  日期：2006.2

  Et2AlCN in the presence of Yb(OTf)3 take place in a completely stereoselective manner, demonstrating the efficiency of the sulfinyl group in the control of the stereoselectivity of 1,5-asymmetric hydrocyanation processes as well as the ability of Yb(OTf)3 to form chelated species with ketosulfoxides. The behavior of their methyl derivatives at the benzylic position is dependent on the configuration at

  在Yb（OTf）3存在下，（2-对甲苯基亚磺酰基）苄基烷基（和芳基）酮（δ-酮亚砜）与Et 2 AlCN的反应以完全立体选择性的方式进行，证明了亚砜基在1，5-不对称氢氰化过程的立体选择性的控制以及Yb（OTf）3与酮亚砜形成螯合物种的能力。它们的甲基衍生物在苄基位置的行为取决于手性碳的构型。通过CN基团的水解和CS键的氢解，所得的亚磺酰基氰醇很容易转变为α-羟酰胺。
• Efficient <i>trans</i>-Selectivity in the Cyclocondensation of (<i>S</i>)-2-[2-(<i>p</i>-Tolylsulfinyl)phenyl]acetaldehyde with Activated Dienes Catalyzed by Yb(OTf)₃
  作者：José L. García Ruano、M. Ángeles Fernández-Ibáñez、M. Carmen Maestro

  DOI：10.1021/jo061128n

  日期：2006.9.1

  Reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde 1 with Danishefsky's and related dienes took place in the presence of Yb(OTf)(3) in a completely stereoselective manner, mediated by a remote sulfinyl group (1,5-asymmetric induction), to afford the corresponding 2,3-dihydro-4H-pyran-4-ones. These reactions followed a stepwise mechanism, as was corroborated by isolation of the corresponding intermediates, with a high level of trans-selectivity for 4-methyl-substituted dienes. Treatment of the adducts with Raney Ni provided concomitant cleavage of the C-S bond and reduction of the conjugated carbonyl grouping.
• Synthesis of chiral ortho-(p-tolylsulfinyl) benzyl ketones
  作者：José L. García Ruano、José Alemán、M. Teresa Aranda、M. Ángeles Fernández-Ibáñez、M. Mercedes Rodríguez-Fernández、M. Carmen Maestro

  DOI：10.1016/j.tet.2004.07.050

  日期：2004.10

  (S)-ortho-(p-Tolylsulfinyl)benzyl alkyl (and aryl) ketones 1a–e were prepared in good yields by reaction of esters or nitriles with the lithium benzyl carbanion derived from 2-(p-tolylsulfinyl) methylbenzene. α-Methylbenzyl ketones 2 were prepared as ca. 1:1 diastereoisomeric mixtures by methylation of the unsubstituted ketones 1 with NaH/MeI. The use of the ethylbenzene derivative as the starting

  通过酯或腈与衍生自2-（对甲苯基亚磺酰基）甲基苯的苄基碳负离子的反应，可以高收率制备（S）-邻-（对甲苯基亚磺酰基）苄基烷基（和芳基）酮1a - e。制备α-甲基苄基酮2。通过用NaH / MeI甲基化未取代的酮1形成1：1的非对映异构体混合物。使用乙苯衍生物作为起始原料得到复杂的混合物。纯（S，（S）S）-2的遵守非对映异构体可以通过用PCC氧化由醛与衍生自2-（对甲苯基亚磺酰基）乙苯的锂碳负离子反应得到的醇（羟基碳上的异构体混合物）而以高收率获得。