(S)-2,2,3-triphenyloxirane | 157556-88-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (S)-2,2,3-triphenyloxirane
• 英文别名: (S)-triphenylethylene oxide；2,2,3-triphenyloxirane；Oxirane, triphenyl-, (3S)-；(3S)-2,2,3-triphenyloxirane
• CAS: 157556-88-2
• 化学式: C₂₀H₁₆O
• 分子量: 272.346
• InChiKey: LJYNYLMLKGMXCC-IBGZPJMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-2,2,3-triphenyloxirane 在 palladium on activated charcoal Ti(N3)2(OiPr)2 、 硫酸 、 氢气 、 potassium carbonate 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 59.5h， 生成 (S)-2-(1,3-dihydroisoindol-2-yl)-1,2,2-triphenylethanol
  参考文献：
  名称：

  Highly Efficient Synthesis of Enantiomerically Pure (S)-2-Amino-1,2,2-triphenylethanol. Development of a New Family of Ligands for the Highly Enantioselective Catalytic Ethylation of Aldehydes

  摘要：

  The reaction of (S)-triphenylethylene oxide (3) with diisopropoxytitanium(IV) diazide in benzene solution at 70 degrees C takes place readily in a completely regioselective and stereospecific manner to afford (S)-2-azido-1,2,2-triphenylethanol (6). Reduction of the azide by catalytic hydrogenation leads to (S)-2-amino-1,2,2-triphenylethanol (5) that, by N,N-dialkylation with 1,4-dibromobutane, 1,5-dibromopentane, 1,5-dibromo-3-oxapentane, alpha,alpha'- dibromo-o-xylene, and methyl iodide, affords the corresponding (S)-2-dialkylamina-1,2,2-triphenylethanols (7a-e). On the other hand, the reaction of 5 with benzyl bromide or 1-iodobutane takes place as a monoalkylation, leading to the corresponding (S)-2-alkylamino-1,2,2-triphenylethanols (8f,g). The performance of amino alcohols 7a-e as ligands for the catalytic enantioselective addition of diethylzinc to benzaldehyde has been studied, with enantioselectivities of 94-97% being recorded. The best performing ligands in this family; 7a [(S)-1,2,2-triphenyl-2-(1-pynolidinyl)-ethanol] and 7c [(S)-2-morpholino-1,2,2-triphenylethanol] have been studied in the addition of Et2Zn to a representative family of aldehydes. With 7a, a 96.6% mean ee is recorded for a family of 16 alpha-substituted aldehydes and a 92.8% mean ee for a family of six alpha-unsubstituted aldehydes. With 7c working on the same families of aldehydes, the mean enantioselectivities are 96.8% and 91.8%, respectively.

  DOI：

  10.1021/jo982442n
• 作为产物：
  描述：

  三苯乙烯 在 sodium hypochlorite 、 4-苯基吡啶-N-氧化物 、 (-)-chloro((1R,2R)-4,4',6,6'-tetra-tert-butyl-2,2'-[cyclohexane-1,2-diylbis(nitrilomethylidyne)]diphenolato)manganese(III) 、 水 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以71%的产率得到(S)-2,2,3-triphenyloxirane
  参考文献：
  名称：

  Continuous flow enantioselective arylation of aldehydes with ArZnEt using triarylboroxins as the ultimate source of aryl groups

  摘要：

  本文描述了一种从醛合成对映富集二芳基甲醇的连续流动系统。该系统使用氨基醇功能化的聚苯乙烯树脂作为催化剂，芳基化试剂通过三芳基硼烷与二乙基锌的转金属化方便地制备。

  DOI：

  10.3762/bjoc.5.56

文献信息

• Accessible sugars as asymmetric olefin epoxidation organocatalysts: glucosaminide ketones in the synthesis of terminal epoxides
  作者：Omar Boutureira、Joanna F. McGouran、Robert L. Stafford、Daniel P. G. Emmerson、Benjamin G. Davis

  DOI：10.1039/b911675c

  日期：——

  A systematically varied series of conformationally restricted ketones, readily prepared from N-acetyl-D-glucosamine, were tested against representative olefins as asymmetric epoxidation catalysts showing useful selectivities against terminal olefins and, in particular, typically difficult 2,2-disubstituted terminal olefins.

  一系列系统变化的构象限制酮，很容易从 N-乙酰基-D-氨基葡萄糖对作为不对称环氧化催化剂的代表性烯烃进行了测试，显示出对末端烯烃的有用选择性，特别是典型的难处理的 2,2-二取代末端烯烃。
• Catalytic asymmetric epoxidation of alkenes with arabinose-derived uloses
  作者：Tony K.M Shing、Yiu C Leung、Kwan W Yeung

  DOI：10.1016/s0040-4020(03)00145-5

  日期：2003.3

  Four l-erythro-2-uloses were readily prepared from l-arabinose via a reaction sequence involving Fischer glycosidation, acetalization and oxidation. Bulky steric sensors at the anomeric center could enhance the stereoselectivity of the dioxirane epoxidation and one of the uloses performed with good enantioselectivity towards trans-stilbene (up to 90% ee). However, the catalysts decomposed during the

  四个1-赤-2- uloses从L-阿拉伯糖通过涉及费歇尔糖苷化，缩醛化和氧化的反应序列中容易地制备。在异头异构中心的庞大空间传感器可以增强二环氧乙烷环氧化的立体选择性，并且其中一种对高二苯乙烯的对映体选择性（最高90％ee）。然而，在碱性条件下，环氧化过程中催化剂分解，最大化学收率仅为13％。三1-苏-3-果糖可以克服酯基团α对酮官能团的吸电子作用而产生的分解问题。使用带有两个侧酯基的酮，最佳化学收率可达93％。一种改进的果糖对反式二取代和三取代的烯烃表现出中等的对映选择性（40-68％ee）。
• Arabinose-Derived Ketones as Catalysts for Asymmetric Epoxidation of Alkenes
  作者：Tony K. M. Shing、Gulice Y. C. Leung、To Luk

  DOI：10.1021/jo050928f

  日期：2005.9.1

  Readily available arabinose-derived ketones, containing a tunable butane-2,3-diacetal as the steric blocker, displayed increasing enantioselectivity (up to 90% ee) with the size of the acetal alkyl group in catalytic asymmetric epoxidation of trans-disubstituted and trisubstituted alkenes. The stereochemical communication between our ketone catalysts and the alkene substrates is mainly due to steric

  现成的阿拉伯糖衍生的酮，包含可调节的2,3-丁烷作为空间阻滞剂，在反式-二取代和三取代的催化不对称环氧化反应中，随着乙缩醛烷基大小的增加，对映选择性增加（最多90％ee）。烯烃。我们的酮催化剂与烯烃底物之间的立体化学连通主要是由于空间效应，而涉及底物和催化剂的苯基之间的π-π相互作用的电子效应在我们的系统中似乎不起作用。
• Asymmetric Epoxidation Using Iminium Salt Organocatalysts Featuring Dynamically Controlled Atropoisomerism
  作者：Philip C. Bulman Page、Christopher J. Bartlett、Yohan Chan、David Day、Phillip Parker、Benjamin R. Buckley、Geracimos A. Rassias、Alexandra M. Z. Slawin、Steven M. Allin、Jérôme Lacour、André Pinto

  DOI：10.1021/jo300915u

  日期：2012.7.20

  Introduction of a pseudoaxial substituent at a stereogenic center adjacent to the nitrogen atom in binaphthyl- and biphenyl-derived azepinium salt organocatalysts affords improved enantioselectivities and yields in the epoxidation of unfunctionalized alkenes. In the biphenyl-derived catalysts, the atropoisomerism at the biphenyl axis is controlled by the interaction of this substituent with the chiral

  在衍生自双萘基和联苯的氮杂吡啶鎓盐有机催化剂中与氮原子相邻的立体中心处引入假轴取代基，可提高对映选择性，并提高未官能化烯烃的环氧化收率。在联苯衍生的催化剂中，联苯轴上的对映异构通过该取代基与氮上的手性取代基的相互作用来控制。
• Highly Enantioselective Reaction of α-Selenoorganolithium Compounds with Chiral Bis(oxazoline)s and Preparation of Enantioenriched Benzylidencyclohexanes
  作者：Shuichi Nakamura、Takayuki Aoki、Takahiro Ogura、Libo Wang、Takeshi Toru

  DOI：10.1021/jo048505l

  日期：2004.12.1

  The enantioselective reaction of α-seleno carbanions derived from bis(phenylseleno)acetal and bis(2-pyridylseleno)acetal in the presence of bis(oxazoline)s with various electrophiles gave products with high enantioselectivity. The enantioselective reaction of α-lithio benzyl 2-pyridyl selenide gave the products with stereochemistry reverse to that obtained in the reaction of α-lithio benzyl phenyl

  在双（恶唑啉）存在下，由双（苯基硒基）缩醛和双（2-吡啶基硒基）缩醛衍生的α-硒基碳负离子与各种亲电试剂的对映选择性反应得到高对映选择性的产物。α-亚硫基苄基2-吡啶基硒化物的对映选择性反应产生的产物的立体化学与α-亚硫基苄基苯基硒化物的反应相反。机理研究表明，在-78°C下这些反应的对映体测定取决于动态热力学分辨率。将对映选择性反应用于制备富含对映体的烯烃和环氧化物。