(S)-2-(p-tolylsulfinyl)benzaldehyde | 861942-71-4

• 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-(p-tolylsulfinyl)benzaldehyde
• 英文别名: 2-[(S)-(4-methylphenyl)sulfinyl]benzaldehyde
• CAS: 861942-71-4
• 化学式: C₁₄H₁₂O₂S
• 分子量: 244.314
• InChiKey: UYKMNCUZZGXVQU-KRWDZBQOSA-N

物化性质

• 熔点：
  87-91 °C(Solv: hexane (110-54-3))
• 沸点：
  434.4±38.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 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-(p-tolylsulfinyl)benzaldehyde 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 正丁基锂 、 sodium hydride 、 caesium carbonate 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 反应 2.17h， 生成 1,3-dimethoxy-2-[(S)-methoxy-(2-methylphenyl)methyl]benzene
  参考文献：
  名称：

  The first stereoselective Pd-catalyzed addition of boronic acids onto aldehydes

  摘要：

  The coupling reaction between 2-p-totylsulfinyl benzaldehyde and substituted boronic acids catalyzed by Pd-2(dba)(3)center dot CHCL3 proceeds in a stereoselective manner, demonstrating the efficiency of the sulfinyl group as a chiral inductor. Enantiopure secondary diaryl alcohols become easily accessible by subsequent sulfoxide-lithium exchange. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2007.06.031
• 作为产物：
  描述：

  (S)-2-(p-tolylsulfinyl)benzaldehyde diethyl acetal 在 4-甲基苯磺酸吡啶 作用下， 以 水 、 丙酮 为溶剂， 反应 4.0h， 以82%的产率得到(S)-2-(p-tolylsulfinyl)benzaldehyde
  参考文献：
  名称：

  The first stereoselective Pd-catalyzed addition of boronic acids onto aldehydes

  摘要：

  The coupling reaction between 2-p-totylsulfinyl benzaldehyde and substituted boronic acids catalyzed by Pd-2(dba)(3)center dot CHCL3 proceeds in a stereoselective manner, demonstrating the efficiency of the sulfinyl group as a chiral inductor. Enantiopure secondary diaryl alcohols become easily accessible by subsequent sulfoxide-lithium exchange. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2007.06.031

文献信息

• Asymmetric [2,3]-Wittig Rearrangement: Synthesis of Homoallylic, Allenylic, and Enynyl α-Benzyl Alcohols
  作者：Ricardo I. Rodríguez、Elsie Ramírez、José A. Fernández-Salas、Rubén Sánchez-Obregón、Francisco Yuste、José Alemán

  DOI：10.1021/acs.orglett.8b03659

  日期：2018.12.21

  A highly stereoselective [2,3]-Wittig rearrangement of allylic and propargylic ethers controlled by a chiral sulfoxide moiety is presented. The activation provided by the sulfoxide at the remote ortho position allows the rearrangement of less-activated and unexplored benzylic carbanions. Thus, this general methodology gives access to the asymmetric synthesis of homoallylic, enynyl, and allenylic α-benzyl

  呈现了由手性亚砜部分控制的烯丙基和炔丙基醚的高度立体选择性[2,3] -Wittig重排。亚砜在遥远的邻位提供的活化作用使未活化和未开发的苄基碳负离子得以重排。因此，这种通用方法使不对称合成均烯丙基，烯丙基和烯丙基α-苄醇衍生物成为可能。
• Influence of an ortho-sulfinyl group on the configurational stability of α-lithiated aryloxiranes: deuteration of tolylsulfinyl styrene oxides
  作者：Vito Capriati、Saverio Florio、Renzo Luisi、Antonio Salomone、Maria Giovanna Tocco、Ana M. Martín Castro、José Luis García Ruano、Esther Torrente

  DOI：10.1016/j.tet.2008.10.021

  日期：2009.1

  and stereoselectivity of the deuteration reactions of substituted styrene oxides has been investigated. The sulfinyl group at an ortho-position reduces the configurational stability of α-lithiated styrene oxides, whereas meta- and para-sulfinyl derivatives completely control the regioselectivity only yielding deuterated products at the aromatic ring due to its strong ortho-director effect.

  研究了位于邻位，间位和对位的对甲苯亚磺酰基对取代苯乙烯氧化物的氘代反应的区域选择性和立体选择性的影响。在邻位的亚磺酰基降低了α-锂化的苯乙烯氧化物的构型稳定性，而间-和对-亚磺酰基衍生物完全控制区域选择性，由于其强大的邻位导向作用，仅在芳族环上产生氘代产物。
• Remote stereocontrol by the sulfinyl group. Diels–Alder reaction of cyclopentadiene with substituted (S)-[2-(p-tolylsulfinyl)styrenes and (S)-[2-(p-tolylsulfinyl)phenyl] vinyl ketones
  作者：M. Carmen Maestro、José Antonio Fernández-Salas、José L. García Ruano、Oney O. Ramírez-Rodríguez、Ramiro Araya-Maturana

  DOI：10.1016/j.tet.2012.03.112

  日期：2012.6

  a homochiral sulfinyl group at the dienophile to act as a remote stereocontrol inductor in the Diels–Alder reaction with cyclopentadiene has been evaluated. High pressure conditions were required for the reactions of (S)-2-(p-tolylsulfinyl)styrenes 3–5 (E-1,2-disubstituted double bond) and 6–8 (1,1-disubstituted double bond). A good facial selectivity and total endo selectivity were attained with 1

  在亲二烯体上的同手性亚磺酰基作为Diels-Alder与环戊二烯反应的远程立体控制诱导剂的能力已得到评估。被要求为（反应高压条件小号）-2-（p -tolylsulfinyl）苯乙烯3 - 5（Ë -1,2-二取代的双键）和6 - 8（1,1-二取代的双键）。用1，1-二取代的亲二烯物获得了良好的面部选择性和总的内在选择性，尽管1，2-二取代的亲二物物的结果较差。相反，（S）-[2-（对甲苯基亚磺酰基）苯基]乙烯基酮9– 11在作为亚磺酰基和羰基氧原子螯合剂的Yb（OTf）3的存在下，在低温（−40°C）下具有完全的内在选择性和高的面部选择性，易于反应。关于呋喃反应，在路易斯酸存在下，β-三氟甲基烯酮14可提供具有高面部选择性的Diels-Alder加合物，但是β-非取代的烯酮9和12产生了呋喃共轭物加成双键的产物。
• Organocatalytic asymmetric deoxygenation of sulfones to access chiral sulfinyl compounds
  作者：Shengli Huang、Zhen Zeng、Nan Zhang、Wenling Qin、Yu Lan、Hailong Yan

  DOI：10.1038/s41557-022-01120-x

  日期：2023.2

  incorporation of a cyano group into the sulfone generates a chiral sulfinic species as an active intermediate. A wide range of chiral sulfinates with high enantioselectivities could then be acquired using alcohols as nucleophiles, and the subsequent transformations allowed the collective preparation of a variety of chiral sulfinyl compounds. Density functional theory calculations revealed that the catalytic cycle

  在过去的几十年里，已经开发了许多有效的方法，可以实现手性亚磺酰化合物的对映选择性合成。然而，六价砜的对映选择性脱氧以形成手性亚磺酰基化合物仍然是不对称合成和有机硫化学领域的主要挑战之一。在这里，我们已经证明有机催化和将氰基结合到砜中的协同组合产生手性亚磺酸物种作为活性中间体。然后可以使用醇作为亲核试剂获得各种具有高对映选择性的手性亚磺酸盐，随后的转化允许集体制备各种手性亚磺酰基化合物。密度泛函理论计算表明，催化循环涉及奎宁环辅助的逐步1,2-氰基转移、碱辅助的醇分子间取代和活性催化剂的再生。对映选择性由氰基迁移步骤确定。
• Stereoselective Quaternization of α-Amino Phenylacetonitriles Mediated by a Remote Sulfinyl Group
  作者：José Luis García Ruano、Ana M. Martín-Castro、Francisco Tato、Inés Alonso

  DOI：10.1021/jo0705519

  日期：2007.8.1

  Enantiomerically pure alpha-substituted alpha-amino phenylacetonitriles have been readily prepared from 2-p-tolylsulfinylbenzaldimines following a two-step sequence: a moderately stereoselective hydrocyanation of the imines and a completely stereoselective quaternization of the resulting diastereoisomeric mixture of alpha-amino phenylacetonitriles with different alkylating or acylating reagents in the presence of KHMDS. Theoretical calculations support a stereoselectivity control exerted by the remote sulfinyl group, as long as it is responsible for the conformational preferences of the benzyllithium intermediates, which suffer the attack of the electrophiles to the less hindered diastereotopic face.