(R,R)-3-phenyloxiraneethanol

• 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: (R,R)-3-phenyloxiraneethanol
• 英文别名: 2-[(2R,3R)-3-phenyloxiran-2-yl]ethanol
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: ZCNFBAJNMACHSZ-NXEZZACHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  32.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,4-二氯碘苯 、 (R,R)-3-phenyloxiraneethanol 在 吡啶 、 N,N-二甲基丙烯基脲 、 锰 、 [nickel(II)dichloride(dimethoxyethane)] 、 C₁₈H₃₆N₂O₄Si₂ 、 三乙胺盐酸盐 、 sodium iodide 作用下， 反应 12.0h， 以49%的产率得到(3S,4S)-4-(3,4-dichlorophenyl)-4-phenylbutane-1,3-diol
  参考文献：
  名称：

  Nickel Catalyzed Regio-, Diastereo-, and Enantioselective Cross-Coupling of 3,4-Epoxyalcohol with Aryl Iodides

  摘要：

  The first catalytic, regioselective cross-coupling of 3,4-epoxyalcohol with aryl iodides is reported. The combination of NiCl2 center dot DME and a newly developed C-2-symmetric oxazoline ligand plays a key role in selective ring opening of several 3,4-epoxy alcohols at the C4 position. This general protocol furnishes a new type of enantioenriched 4,4-diaryl alkane which also incorporates an additional 1,3-diol that can be easily transformed to a variety of functional groups. The products are formed with excellent regioselectivity (>99:1), diastereoselectivity (up to 99:1), and enantiopurity (up to >99.9% ee).

  DOI：

  10.1021/acs.orglett.7b02076
• 作为产物：
  描述：

  反-苯乙烯乙酸 在 Chiral ketone Oxone 、 lithium aluminium tetrahydride 、 四丁基硫酸氢铵 、 potassium carbonate 作用下， 以 四氢呋喃 、 acetate buffer 、 乙腈 为溶剂， 反应 2.0h， 生成 (R,R)-3-phenyloxiraneethanol
  参考文献：
  名称：

  A pH Study on the Chiral Ketone Catalyzed Asymmetric Epoxidation of Hydroxyalkenes

  摘要：

  A detailed study shows that the chiral ketone catalyzed asymmetric epoxidations of hydroxyalkenes are highly pH dependent. The lower enantioselectivity obtained at low pH is attributed to the substantial contribution of the direct epoxidation by Oxone. At high pH the epoxidation mediated by chiral ketone out-competes the racemic epoxidation, leading to higher enantioselectivity. The effective substrates include allylic alcohol, homoallylic alcohol, and bishomoallylic alcohol. In most cases, over 90% ee was obtained.

  DOI：

  10.1021/jo972106r

文献信息

• Highly Regioselective 5‐ <i>endo‐tet</i> Cyclization of 3,4‐Epoxy Amines into 3‐Hydroxypyrrolidines Catalyzed by La(OTf) ₃
  作者：Yuse Kuriyama、Yusuke Sasano、Yoshihiko Hoshino、Shun‐ichiro Uesugi、Aoto Yamaichi、Yoshiharu Iwabuchi

  DOI：10.1002/chem.202004455

  日期：2021.1.26

  aminolysis of 3,4‐epoxy amines has been achieved. Key features of this reaction are (1) chemoselective activation of epoxides in the presence of unprotected aliphatic amines in the same molecules by a La(OTf)3 catalyst and (2) excellent regioselectivity for anti‐Baldwin 5‐endo‐tet cyclization. This reaction affords 3‐hydroxy‐2‐alkylpyrrolidines stereospecifically in high yields. DFT calculations revealed

  已经实现了3,4-环氧胺的高度区域选择性的分子内氨解。该反应的主要特征是（1）在由拉（OTF）存在下，在相同的分子无保护的脂族胺的环氧化物的化学选择性活化3抗鲍德温-5-催化剂和（2）优良的区位选择性内切- TET环化。该反应可立体高产率提供3-羟基-2-烷基吡咯烷。DFT计算表明，区域选择性可能归因于环氧胺底物的变形能。该反应的使用通过抗痉挛剂溴化芬尼的首次对映选择性合成得到证明。
• Lewis acid-promoted electron transfer deoxygenation of epoxides, sulfoxides, and amine N-oxides: the role of low-valent niobium complexes from NbCl5 and Zn
  作者：Kyungsoo Oh、William Eric Knabe

  DOI：10.1016/j.tet.2009.02.013

  日期：2009.4

  A mild and operationally simple deoxygenation of epoxides, sulfoxides, and amine N-oxides is described using a sub-stoichiometric amount of low-valent niobium complexes generated in situ from commercially available NbCl5 and zinc dust. The deoxygenation proceeds by a reductive cleavage of polarized O–C/O–N/O–S bonds through a single electron transfer from zinc metal to the niobium–substrate complex

  使用亚化学计量量的由市售NbCl 5和锌粉原位生成的低价铌络合物，描述了对环氧化合物，亚砜和胺N-氧化物进行温和且简单的脱氧的方法。由于铌物种的高亲氧性，单价电子从锌金属转移到铌-底物络合物，使极化的O-C / O-N / O-S键还原性裂解，从而进行脱氧。相邻的自由基稳定基团的存在对环氧底物是有利的。但是，类似的前提条件不适用于亚砜和胺N-氧化物，在这些亚胺和N-胺胺中，各种底物均能以优异的产率有效地脱氧。
• Development and application of versatile bis-hydroxamic acids for catalytic asymmetric oxidation
  作者：Allan U. Barlan、Wei Zhang、Hisashi Yamamoto

  DOI：10.1016/j.tet.2007.03.071

  日期：2007.7

  preliminary results of our new designed C(2)-symmetric bis-hydroxamic acid (BHA) ligands and the application of the new ligands for vanadium-catalyzed asymmetric epoxidation of allylic alcohols as well as homoallylic alcohols. From this success we demonstrate the versatile nature of BHA in the molybdenum catalyzed asymmetric oxidation of unfunctionalized olefins and sulfides.

  在本文中，我们描述了我们新设计的 C(2)-对称双异羟肟酸 (BHA) 配体的开发和初步结果，以及新配体在钒催化烯丙醇和高烯丙醇不对称环氧化中的应用. 从这一成功中，我们证明了 BHA 在钼催化的非官能化烯烃和硫化物的不对称氧化中的多功能性。
• Regioselective nucleophilic ring opening of epoxides and aziridines derived from homoallylic alcohols
  作者：David Tanner、Thomas Groth

  DOI：10.1016/s0040-4020(97)10053-9

  日期：1997.11

  of the nucleophile to C-3 via a six-membered transition state, leading to 1,4-diols or 1,4-amino alcohol derivatives. In general, the epoxy alcohols gave poorer regioselectivity than the N-tosyl aziridino alcohols, for which selectivities of >95:5 were routinely obtained. The activating effect of a phenyl group at C-4 led to a switch in regiochemistry, with the 1,3-diol or 1,3-amino alcohol derivative

  研究了一些3,4-环氧和3,4-叠氮基醇的亲核开环的区域选择性。选择的亲核试剂是复合氢化物（LiAlH 4，Red-Al和DIBAL）和Lipshutz型或Gilman型有机铜酸盐试剂。改变底物中的C-4取代基以研究空间和电子对开环反应的影响。对于C-4处的烷基取代基，大部分结果可以基于亲核试剂通过六元过渡态分子内递送至C-3的结果来解释，从而生成1,4-二醇或1,4-氨基醇衍生品。通常，环氧醇比N的区域选择性差-甲苯磺酰基叠氮基醇，通常获得> 95：5的选择性。C-4上的苯基的活化作用导致区域化学发生了变化，以1,3-二醇或1,3-氨基醇衍生物为主要产物。
• Efficient synthesis of asymmetric epoxidation catalyst I
  申请人：Institut Catala D'Investigacio Quimica

  公开号：EP1770094A1

  公开（公告）日：2007-04-04

  A process for the preparation of chiral ketone I from diol II comprising the acetylation of diol II with an acetylating agent, preferably an acetic acid derivative, wherein said acetylation is performed in the presence of a Lewis acid. The process can further comprise additional previous steps, so that chiral ketone I can be prepared in four steps starting from D-fructose. Alternatively, a process for the preparation of chiral ketone V from diol VI comprising the acetylation of diol VI with an acetylating agent, preferably an acetic acid derivative, wherein said acetylation is performed in the presence of a Lewis acid. The process can further comprise additional previous steps, so that chiral ketone V can be prepared starting from L-fructose, L-sorbose or D-arabinose.

  一种从二醇II制备手性酮I的方法，包括使用乙酰化剂（优选为乙酸衍生物）对二醇II进行乙酰化，其中所述乙酰化是在Lewis酸存在下进行的。该方法还可以包括额外的先前步骤，以便从D-果糖开始，经过四个步骤制备手性酮I。另一种方法是从二醇VI制备手性酮V的方法，包括使用乙酰化剂（优选为乙酸衍生物）对二醇VI进行乙酰化，其中所述乙酰化是在Lewis酸存在下进行的。该方法还可以包括额外的先前步骤，以便从L-果糖、L-山梨糖或D-阿拉伯糖开始制备手性酮V。