(S)-1-(2-(p-tolylsulfinyl)phenyl)ethanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-1-(2-(p-tolylsulfinyl)phenyl)ethanone
• 英文别名: (S)-1-[2-(p-tolylsulfinyl)phenyl]ethanone；methyl 2-[(p-tolylsulfinyl)phenyl]ketone；1-[2-[(S)-(4-methylphenyl)sulfinyl]phenyl]ethanone
• 化学式: C₁₅H₁₄O₂S
• 分子量: 258.341
• InChiKey: NUBJUEOFVJUGBX-SFHVURJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  3
• 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)-1-(2-(p-tolylsulfinyl)phenyl)ethanone 在 甲基锂 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.67h， 生成 (R)-3-methyl-3-(phenylethynyl)isobenzofuran-1(3H)-one
  参考文献：
  名称：

  Asymmetric Synthesis of Tertiary Benzylic Alcohols

  摘要：

  Vinyl, aryl, and alkynyl organometallics add to ketones containing a stereogenic sulfoxide. Tertiary alcohols are generated in diastereomerically and enantiomerically pure form. Reductive lithiation converts the sulfoxide into a variety of useful functional groups.

  DOI：

  10.1021/ol102567h
• 作为产物：
  描述：

  2-(2-溴苯基)-2-甲基-1,3-二氧戊环 在 正丁基锂 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 正己烷 、 水 、 丙酮 为溶剂， 反应 7.67h， 生成 (S)-1-(2-(p-tolylsulfinyl)phenyl)ethanone
  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

• Chiral Allene-Containing Phosphines in Asymmetric Catalysis
  作者：Feng Cai、Xiaotao Pu、Xiangbing Qi、Vincent Lynch、Akella Radha、Joseph M. Ready

  DOI：10.1021/ja207748r

  日期：2011.11.16

  metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of arylboronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals, generating bi- and tridentate ligands.

  我们证明了丙二烯，手性 1,2-二烯，附加有基本功能可以作为过渡金属的配体。我们描述了一种含丙二烯的双膦，当与 Rh(I) 配位时，可促进芳基硼酸以高对映选择性不对称加成到 α-酮酯。溶液和固态结构分析表明丙二烯的一种烯烃可以与过渡金属配位，生成双齿和三齿配体。
• 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。
• New Strategy for the Asymmetric Synthesis of Phenyl Ketone Cyanohydrins:  Quaternization of Cyanohydrins Derived from 2-<i>p</i>-Tolylsulfinyl Benzaldehyde
  作者：José Luis García Ruano、Ana M. Martín-Castro、Francisco Tato、César J. Pastor

  DOI：10.1021/jo051029u

  日期：2005.9.1

  Optically pure functionalized cyanohydrins derived from 1-[2-(p-tolylsulfinyl)phenyl] ethanone can be obtained by the reaction of 2-p-tolylsulfinyl benzaldehyde derived cyanohydrins with bases and further treatment with suitable electrophiles. High yields and excellent stereoselectivities (up to de >98%) were obtained for these remote 1,4-asymmetric induction processes controlled by a sulfinyl chiral

  衍生自1- [2-（对甲苯基亚砜基）苯基]乙酮的光学纯的官能化氰醇可通过使2-对甲苯基亚砜基苯甲醛衍生的氰醇与碱反应并用合适的亲电子试剂进一步处理而获得。对于这些由亚硫酰基手性感应剂控制的远程1,4-不对称感应过程，获得了高收率和出色的立体选择性（高达de> 98％）。
• 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.
• The first stereoselective Pd-catalyzed addition of boronic acids onto aldehydes
  作者：Alexandra Novodomskà、Mària Dudičovà、Frédéric R. Leroux、Françoise Colobert

  DOI：10.1016/j.tetasy.2007.06.031

  日期：2007.7

  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.