tert-butyl 2,2-dimethyl-4-[(E)-2-phenylethenyl]-1,3-oxazolane-3-carboxylate | 132652-65-4

• 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: tert-butyl 2,2-dimethyl-4-[(E)-2-phenylethenyl]-1,3-oxazolane-3-carboxylate
• 英文别名: tert-butyl (E)-2,2-dimethyl-4-(2'-phenylvinyl)-3-oxazolidinecarboxylate；tert-butyl (4R)-2,2-dimethyl-4-[(E)-2-phenylethenyl]-1,3-oxazolidine-3-carboxylate
• CAS: 132652-65-4
• 化学式: C₁₈H₂₅NO₃
• 分子量: 303.401
• InChiKey: YGWQOVWQQNBLIS-AYJWMTRPSA-N

物化性质

• 沸点：
  412.4±45.0 °C(predicted)
• 密度：
  1.105±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl 2,2-dimethyl-4-[(E)-2-phenylethenyl]-1,3-oxazolane-3-carboxylate 在 palladium on activated charcoal 氢气 、 对甲苯磺酸 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 48.0h， 生成 N-Boc-D-homophenylalaninol
  参考文献：
  名称：

  Synthetic Elaboration of the Side Chain of (R)-2,2-Dimethyl-3-(tert-butoxycarbonyl)-4-ethynyloxazolidine:  A New Regio- and Stereoselective Strategy to δ-Functionalized β-Amino Alcohols

  摘要：

  An investigation of the reactivity of ethynyloxazolidine 2 is presented. Functionalization at the acetylenic position has been found to occur very easily using the mild Sonogashira conditions. Addition of tributyltin cuprate 1 provided the corresponding stannylated (E)-ethenyloxazolidine 3, a new chiral building block which has been reacted with electrophiles under Pd catalysis. The reaction sequence occurred without racemization and showed an easy and mild procedure for the regio- and stereoselective synthesis of unsaturated amino alcohols.

  DOI：

  10.1021/jo970619s
• 作为产物：
  描述：

  tert-butyl (Z)-2,2-dimethyl-4-(2'-phenylvinyl)-3-oxazolidinecarboxylate 在 偶氮二异丁腈 、 苯硫酚 作用下， 以 苯 为溶剂， 反应 16.0h， 以2.0 g的产率得到tert-butyl 2,2-dimethyl-4-[(E)-2-phenylethenyl]-1,3-oxazolane-3-carboxylate
  参考文献：
  名称：

  Regio- and stereoselective synthesis of 1,3-aminoalcohol derivatives from allylamine derivatives via internal sulfinyl group participation

  摘要：

  The regio- and stereoselective preparation of 1,3-aminoalcohol derivatives from protected allylamines via intramolecular participation by the sulfinyl group is reported. A carbamate protecting group on nitrogen leads to products arising from nucleophilic participation by both the sulfinyl and carbamate groups, while protection as the sulfonamide affords the product arising from sulfinyl group participation alone. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.11.036

文献信息

• Elaboration of the side-chain of amino acid derivatives by palladium catalysed couplings
  作者：Geoffrey T. Crisp、Yu-Lin Jiang、Peter J. Pullman、Chris De Savi

  DOI：10.1016/s0040-4020(97)10197-1

  日期：1997.12

  The palladium-catalysed couplings of aryl halides and triflates with propargyl amino amides and the couplings of aryl and vinyl halides and triflates with an ethynyl oxazolidine are reported.

  据报道，钯催化的芳基卤化物和三氟甲磺酸酯与炔丙基氨基酰胺的偶合以及芳基和乙烯基卤化物和三氟甲磺酸酯与乙炔基恶唑烷的偶合。
• A short and efficient synthesis of phytosphingosines using asymmetric dihydroxylation
  作者：Ritsuo Imashiro、Osamu Sakurai、Toyoharu Yamashita、Hiroshi Horikawa

  DOI：10.1016/s0040-4020(98)00615-2

  日期：1998.9

  A short synthesis of the phytosphingosine derivatives and their stereoisomers by using asymmetric dihydroxylation of the optically active olefins derived from l-serine is described.

  描述了通过使用衍生自1-丝氨酸的旋光性烯烃的不对称二羟基化来简短合成植物鞘氨醇衍生物及其立体异构体。
• (2<i>R</i>,1‘<i>S</i>,2‘<i>R</i>,3‘<i>S</i>)-2-(2‘-Carboxy-3‘-phenylcyclopropyl)glycine (PCCG-13), the First Potent and Selective Competitive Antagonist of Phospholipase D-Coupled Metabotropic Glutamate Receptors:  Asymmetric Synthesis and Preliminary Biological Properties
  作者：Roberto Pellicciari、Maura Marinozzi、Gabriele Costantino、Benedetto Natalini、Flavio Moroni、Domenico Pellegrini-Giampietro

  DOI：10.1021/jm990128v

  日期：1999.7.1

  The asymmetric synthesis of (2R,1'S,2'R, 3'S)-2-(2'-carboxy-3'-phenylcyclopropyl)glycine (PCCG-13), a trisubstituted carboxycyclopropylglycine endowed with unusual stereochemical features, is described. Preliminary biological evaluation demonstrates PCCG-13 as a very potent and selective competitive antagonist for the novel class of metabotropic glutamate (mGlu) receptors coupled to the activity of

  描述了不对称合成的（2R，1'S，2'R，3'S）-2-（2'-羧基-3'-苯基环丙基）甘氨酸（PCCG-13），一种具有不同立体化学特征的三取代羧基环丙基甘氨酸。初步生物学评估表明，PCCG-13是与磷脂酶D（PLD）活性偶联的新型代谢型谷氨酸（mGlu）受体的非常有效和选择性的竞争性拮抗剂。因此，PCCG-13是探索这种新型受体的生理病理作用的有用工具。
• Synthesis of asymmetric (E)-α-–phenyl(ethyl)cyclopropylλycines from serine by diastereoselective dibromocylopropanation
  作者：Ma Pilar de Frutos、Ma Dolores Fernández、E. Fernández-Alvarez、Manuel Bernabé*

  DOI：10.1016/s0040-4020(01)88208-9

  日期：1992.1

  An asymmetric synthesis of (E)-α-(2-phenylcyclopropyl)glycines and also of a homolog of allocoronamic acid, namely (E)-α-(2-ethylcyclopropyl)glycine, is reported. The key step is the dibromocyclopropanation of tert-butyl (E, 4R)- or (E, 4)-2,2-dimethyl-4-(2′-phenylvinyl)- and -(2′-ethylvinyl)-3-oxazolidinecarboxylates, easily prepared from L- or D- serine. This reaction gives good diastereomeric ratios

  报道了（E）-α-（2-苯基环丙基）甘氨酸的不对称合成，以及正膦酸的同系物，即（E）-α-（2-乙基环丙基）甘氨酸的不对称合成。关键步骤是（E，4R）-或（E，4）-2,2-二甲基-4-（2'-苯基乙烯基）-和-（2'-乙基乙烯基）-3-恶唑烷羧酸酯的叔丁基二溴环丙烷化，可轻松从L-或D-丝氨酸制备。该反应给出了良好的非对映异构体比例的二溴环丙烷。分三步将主要化合物转化为相应的环丙基氨基酸。
• Photoexcited Chiral Copper Complex-Mediated Alkene <i>E</i> → <i>Z</i> Isomerization Enables Kinetic Resolution
  作者：Hao Zhang、Congcong Huang、Xiang-Ai Yuan、Shouyun Yu

  DOI：10.1021/jacs.2c04040

  日期：2022.6.22

  2-styrylpyrrolidines. This process is difficult to realize under thermal conditions. Mechanistic experiments and density functional theory (DFT) calculations revealed that different overall sensitization rates of the substrate–catalyst complex of the two enantiomers led to the observed excellent kinetic resolution efficiency. This photochemical transformation expands the potential of kinetic resolution beyond

  虽然不对称合成已被确立为以最有效和最实用的方式构建多功能对映体富集分子的强大合成工具，但外消旋体的拆分仍然是合成手性化合物的最普遍的工业方法。然而，通过外消旋E-烯烃的催化非酶动力学拆分直接形成对映纯Z-异构体仍然具有挑战性。在此，我们公开了一种前所未有的对映选择性E → Z由光激发的手性铜络合物介导的异构化。该催化系统能够实现 2-苯乙烯基吡咯烷的动力学拆分。这个过程在热条件下很难实现。机械实验和密度泛函理论 (DFT) 计算表明，两种对映异构体的底物-催化剂复合物的不同总敏化率导致观察到优异的动力学拆分效率。这种光化学转化扩大了动力学分辨率的潜力，超出了它们已建立的基态反应性，为处于激发态的对映选择性催化提供了一种新的反应模式。