(4S,S_S)-4-Isopropyl-2-<2-(4-methylphenylsulfinyl)phenyl>-4,5-dihydro-1,3-oxazole

• 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: (4S,S_S)-4-Isopropyl-2-<2-(4-methylphenylsulfinyl)phenyl>-4,5-dihydro-1,3-oxazole
• 英文别名: (S)-4-isopropyl-2-(2-((S)-p-tolylsulfinyl)phenyl)-4,5-dihydrooxazole；(S)-4-isopropyl-2-(3-((S)-p-tolylsulfinyl)phenyl)-4,5-dihydrooxazole；(4S)-2-[2-[(S)-(4-methylphenyl)sulfinyl]phenyl]-4-propan-2-yl-4,5-dihydro-1,3-oxazole
• 化学式: C₁₉H₂₁NO₂S
• 分子量: 327.447
• InChiKey: YEHLBWCYEFMSOD-HXOBKFHXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  57.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  间溴苯甲酸 在 正丁基锂 、 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三乙胺 、 对甲苯磺酰氯 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 22.0h， 生成 (4S,S_S)-4-Isopropyl-2-<2-(4-methylphenylsulfinyl)phenyl>-4,5-dihydro-1,3-oxazole
  参考文献：
  名称：

  Branch-Selective Allylic C–H Carboxylation of Terminal Alkenes by Pd/sox Catalyst

  摘要：

  A ligand-controlled branch-selective allylic C-H carboxylation through Pd catalysis is described. The developed catalytic system, which consists of Pd(OAc)(2), sulfoxide oxazoline (sox) as a ligand and benzoquinone as an oxidant, couples terminal alkenes and carboxylic acids to furnish the corresponding branched allylic esters with high regioselectivity.

  DOI：

  10.1021/ol5019135
• 作为试剂：
  描述：

  N-(2-羟基-苯基)-4-甲基-苯磺酰胺 、 天然橡胶 在 氧气 、 palladium diacetate 、 (4S,S_S)-4-Isopropyl-2-<2-(4-methylphenylsulfinyl)phenyl>-4,5-dihydro-1,3-oxazole 作用下， 以 乙腈 为溶剂， 70.0 ℃ 、101.33 kPa 条件下， 反应 20.0h， 生成 2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine 、 3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine
  参考文献：
  名称：

  钯催化的1,3-二烯的不对称氨基羟基化

  摘要：

  利用手性吡啶双（恶唑啉）配体开发了Pd II催化的1,3-二烯与N-甲苯磺酰基-2-氨基苯酚的不对称氨基羟基化反应。高度区域选择性反应可直接高效地获得手性3,4-二氢-2 H -1,4-苯并恶嗪，且产率高且对映选择性高（高达96：4 er）。该反应采用现成的N-甲苯磺酰基-2-氨基苯酚作为独特的氨基羟基化试剂，是已知不对称氨基羟基化方法的补充。

  DOI：

  10.1002/anie.201712350

文献信息

• Sulfoxide ligand metal catalyzed oxidation of olefins
  申请人：The Board of Trustees of the University of Illinois

  公开号：US10266503B1

  公开（公告）日：2019-04-23

  The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C—H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C—H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92% ee, 13 examples ≥90% ee). Additionally, C(sp3)-N fragment coupling reaction between abundant terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/sulfoxide (SOX) catalyzed intermolecular allylic C—H amination is disclosed. A range of 52 allylic amines are furnished in good yields (avg. 76%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). For the first time, a variety of singly activated aromatic and aliphatic nitrogen nucleophiles, including ones with stereochemical elements, can be used in fragment coupling stiochiometries for intermolecular C—H amination reactions.

  通过Pd(II)-催化的烯烃末端前体的烯丙基C—H氧化，已经实现了对异色烷基苯并环的对映选择性合成。这一目标的成功关键在于开发和利用一种新型手性芳基亚砜-噁唑啉（ArSOX）配体。烯丙基C—H氧化反应具有迄今报道的最广泛范围和最高水平的不对称诱导（平均92% ee，13个例子≥90% ee）。此外，通过Pd(II)/亚砜（SOX）催化的分子间烯丙基C—H胺化揭示了丰富的末端烯烃和N-三氟甲磺酰保护的脂肪族和芳香族胺之间的C(sp3)-N片段偶联反应。一系列52种烯丙基胺以良好的产率（平均76%）和优异的区域和立体选择性（平均>20:1线性:支链，>20:1 E:Z）提供。首次，各种单独活化的芳香族和脂肪族氮亲核试剂，包括具有立体化学元素的试剂，可以在分子间C—H胺化反应的片段偶联化学计量中使用。
• Diastereoselective conversion of sulfides into sulfoxides. 1,5- and 1,6-asymmetric induction
  作者：Justin F. Bower、Christopher J. Martin、David J. Rawson、Alexandra M. Z. Slawin、Jonathan M. J. Williams

  DOI：10.1039/p19960000333

  日期：——

  The diastereoselective oxidation of sulfides into sulfoxides has been achieved with enantiomerically pure dihydrooxazole auxiliaries. When an additional hydroxymethyl substituent is present, diastereocontrol is very high and 1,5-asymmetric induction has been achieved with up to 96 : 4 selectivity, and 1,6-asymmetric induction has been achieved with up to 97 : 3 selectivity in the absence of any additional chiral agents.

  用对映纯的二氢噁唑辅基实现了硫化物向亚磺酰胺的非对映选择性氧化。当存在额外的羟甲基取代基时，非对映选择性非常高，1,5-不对称诱导可达到96:4的选择性，而在没有额外的手性试剂的情况下，1,6-不对称诱导可达到97:3的选择性。
• Enantioselective palladium catalysed allylic substitution. Electronic and steric effects of the ligand.
  作者：Joanne V Allen、Justin F Bower、J.M.J. Williams

  DOI：10.1016/s0957-4166(00)86260-6

  日期：1994.10

  Ligands containing an enantiomerically pure oxazoline and a sulfur-containing tether have been examined for their ability to provide asymmetric induction in palladium catalysed allylic substitution reaction. The enantioselectivity obtained was found to be highly dependent upon the stereochemistry at sulfur (for sulfoxides), and also somewhat dependent upon the nature of the aryl group attached to the

  已经检查了包含对映体纯的恶唑啉和含硫的系链的配体在钯催化的烯丙基取代反应中提供不对称诱导的能力。发现获得的对映选择性高度取决于硫（对于亚砜）处的立体化学，并且还取决于与硫连接的芳基的性质。
• Diastereoselective oxidation of arylsulfides
  作者：Justin F Bower、Jonathan Mj Williams

  DOI：10.1016/0040-4039(94)88239-8

  日期：1994.9

  Arylsulfides containing an enantiomerically pure oxazoline in the ortho-position have been oxidised to the corresponding sulfoxides with a variety of reagents. When the oxazoline unit contains a 4-hydroxymethyl group, good levels of diastereocontrol have been obtained using mCPBA (96:4) or t-butylhydroperoxide and titanium tetraisopropoxide (97:3) as the oxidant. This diastereocontrol provides an effective

  在邻位含有对映体纯的恶唑啉的芳基硫醚已用多种试剂氧化为相应的亚砜。当恶唑啉单元包含4-羟甲基时，使用mCPBA（96：4）或叔丁基氢过氧化物和四异丙氧基钛（97：3）作为氧化剂已获得了良好的非对映异构控制水平。这种非对映控制提供了1，6-不对称诱导的有效实例。
• Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C–H Coupling Reaction
  作者：Yoshio Nishimoto、Hiroki Kondo、Kazuya Yamaguchi、Daisuke Yokogawa、Junichiro Yamaguchi、Kenichiro Itami、Stephan Irle

  DOI：10.1021/acs.joc.6b02675

  日期：2017.5.5

  The mechanism of an aromatic C-H coupling reaction between heteroarenes and arylboronic acids using a Pd catalyst was theoretically and experimentally investigated. We identified the C-B transmetalation as the rate determining step. The (S)-catalyst-reactant complex was found to be stabilized by hyperconjugation between pi-orbitals on the tolyl group and the S-O sigma* antibonding orbital in the catalyst ligand. Our findings suggest routes for the design of new, improved Pd catalysts with higher stereoselectivity.