(R)-2-(N-phenyl-aminooxy)-pent-4-en-1-ol | 608130-31-0

• 分子结构分类: 有机化合物 - 苯类化合物 - N-苯基羟胺
• 英文名称: (R)-2-(N-phenyl-aminooxy)-pent-4-en-1-ol
• 英文别名: (2R)-2-(N-phenylaminooxy)pent-4-en-1-ol；(R)-2-(N-phenyl-aminooxy)pent-4-en-1-ol；(R)-2-(N-phenylaminooxy)-pent-4-en-1-ol；(R)-2-((phenylamino)oxy)pent-4-en-1-ol；(R)-2-(N-phenylaminooxy)pent-4-en-1-ol；(R)-2-(N-phenylaminoxy)pent-4-en-1-ol；(2R)-2-anilinooxypent-4-en-1-ol
• CAS: 608130-31-0
• 化学式: C₁₁H₁₅NO₂
• 分子量: 193.246
• InChiKey: SMTALWDEUMJBJE-LLVKDONJSA-N

物化性质

• 沸点：
  311.3±52.0 °C(Predicted)
• 密度：
  1.108±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  41.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-2-(N-phenyl-aminooxy)-pent-4-en-1-ol 在 samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 反应 2.25h， 生成 (R)-pent-4-ene-1,2-diol
  参考文献：
  名称：

  Efficient Asymmetric Syntheses of (+)-Strictifolione

  摘要：

  介绍了 (+)-strictifolione 的不对称合成和正式不对称合成。这两种方法的关键步骤都是通过 Julia-Kocienski 烯化反应生成 E 型烯烃。反-1,3-二醇分子是通过采用 SAMP-腙δ±,δ±′-双烷基化/脱氧协议合成的，而内酯单元的立体中心则是基于面包酵母的酶还原反应。另外，内酯前体也可以通过 (S)- 脯氨酸催化的戊-4-烯醛的δ-氧化反应来有效合成。

  DOI：

  10.1055/s-2004-822387
• 作为产物：
  描述：

  4-戊烯醛 在 sodium tetrahydroborate 作用下， 以 乙醇 、 二氯甲烷 、 氯仿 为溶剂， 反应 3.33h， 生成 (R)-2-(N-phenyl-aminooxy)-pent-4-en-1-ol
  参考文献：
  名称：

  Highly Enantioselective α-Aminoxylation of Aldehydes and Ketones with a Polymer-Supported Organocatalyst

  摘要：

  The first catalytic enantioselective alpha-aminoxylation of aldehydes and ketones using an insoluble, polymer-supported organocatalyst (1) derived from trans-4-hydroxyproline is reported (ee: 96-99%). Reaction rates in the aminoxylation of cyclic ketones with 1 are higher than those reported with L-proline. The insoluble nature of 1 simplifies workup conditions and allows catalyst recycling without an apparent decrease in enantioselectivity or yield.

  DOI：

  10.1021/ol070526p

文献信息

• The Direct Catalytic Asymmetricα-Aminooxylation Reaction: Development of Stereoselective Routes to 1,2-Diols and 1,2-Amino Alcohols and Density Functional Calculations
  作者：Armando Córdova、Henrik Sundén、Anders Bøgevig、Mikael Johansson、Fahmi Himo

  DOI：10.1002/chem.200400137

  日期：2004.8.6

  for the asymmetric alpha-oxidation reaction and found that several proline derivatives were also able to catalyze the transformation with excellent enantioselectivities. Moreover, stereoselective routes for the synthesis of monoprotected vicinal diols and hydroxyketones were found. In addition, short routes for the direct preparation of enantiomerically pure epoxides and 1,2-amino alcohols are presented

  描述了脯氨酸催化的酮和醛的直接不对称α-氨基氧基化。未修饰的酮或醛与亚硝基苯之间的脯氨酸催化反应具有出色的非对映选择性和对映选择性。在所有测试的情况下，分离出的相应产品的ee均> 95％。甲基烷基酮在亚甲基碳原子上被区域特异性氧化，得到对映体纯的α-氨基氧基化酮。另外，环状酮可以以非常高的选择性被α，α'-二氧化，为相应的二氨基氧基化的酮提供大于99％的ee。研究了脯氨酸催化的不对称α-氨氧基化反应的反应机理，为了进一步研究可能的过渡态的性质，我们进行了密度泛函理论（DFT）计算。我们还针对不对称α-氧化反应筛选了其他有机催化剂，发现几种脯氨酸衍生物也能够以出色的对映选择性催化转化。此外，发现了用于合成单保护的邻位二醇和羟基酮的立体选择路线。另外，提出了直接制备对映体纯的环氧化物和1,2-氨基醇的捷径。直接催化的α-氧化也是立体选择性制备β-肾上腺素受体拮抗剂的新途径。我们还针对不对称的α
• PROCESSES OF ENANTIOSELECTIVELY FORMING AN AMINOXY COMPOUND AND AN 1,2-OXAZINE COMPOUND
  申请人：Zhong Guofu

  公开号：US20110224429A1

  公开（公告）日：2011-09-15

  Disclosed is a process of enantioselectively forming an aminoxy compound of Formula (3) In formula (3) R 1 is one of an aliphatic group and an alicyclic group. R 2 is one of hydrogen, an aliphatic group, an alicyclic group, an aromatic group, an arylaliphatic group and an arylalicyclic group. R 3 is one of hydrogen, halogen, hydroxyl, and an aliphatic group with a main chain having 1 to about 10 carbon atoms. The respective aliphatic, alicyclic, aromatic, arylaliphatic or arylalicyclic groups of R 1 , R 2 , and R 3 comprise 0 to about 3 heteroatoms independently selected from the group consisting of N, O, S, Se and Si. The process includes contacting a carbonyl compound of Formula (1) and a nitroso compound of Formula (2) in the presence of a chiral catalyst. The chiral catalyst is a compound of Formula (IX)

  本公开了一种选择性形成化合物的过程，该化合物的化学式为（3）。在化学式（3）中，R1是脂肪族基团和脂环族基团中的一种。R2是氢、脂肪族基团、脂环族基团、芳香族基团、芳基脂肪族基团和芳基脂环族基团中的一种。R3是氢、卤素、羟基和主链含有1至约10个碳原子的脂肪族基团中的一种。R1、R2和R3的各自的脂肪、脂环、芳香、芳基脂肪或芳基脂环基团包括独立选择自N、O、S、Se和Si组成的0至约3个杂原子。该过程包括在手性催化剂的存在下接触化合物的化学式（1）和化合物的化学式（2）。该手性催化剂是化合物的化学式（IX）。
• Prolinate Salts as Catalysts for α-Aminoxylation of Aldehyde and Associated Mechanistic Insights
  作者：Yujiro Hayashi、Nariyoshi Umekubo、Taku Hirama

  DOI：10.1021/acs.orglett.7b01433

  日期：2017.8.18

  Potassium and tetrabutylammonium prolinate salts are efficient catalysts in the α-aminoxylation reaction of aldehydes and nitrosobenzene, to afford synthetically useful chiral α-aminoxylated aldehydes in nearly enantiomerically pure form. This is the first reaction in which prolinate is more reactive and enantioselective than proline. Because of its higher reactivity, the catalyst loading can be reduced

  脯氨酸钾盐和四丁基铵盐是醛和亚硝基苯的α-氨基木糖基化反应中的有效催化剂，以合成几乎对映体纯净形式的合成有用的手性α-氨基木糖基化醛。这是第一个反应，脯氨酸比脯氨酸更具反应性和对映选择性。由于其较高的反应性，可以减少催化剂的负载。提出了一种通过氢键水分子的N-质子化作用活化亚硝基苯的反应机理。
• Highly enantioselective l-thiaproline catalyzed α-aminoxylation of aldehydes in aqueous media
  作者：Pei Juan Chua、Bin Tan、Guofu Zhong

  DOI：10.1039/b817950f

  日期：——

  Highly enantioselective L-thiaproline catalyzed α-aminoxylation of aldehydes in the presence of water and tetrabutylammonium bromide followed by in situreduction to afford the respective α-aminoxy alcohols has been developed in good to high yields (74–88%) and excellent enantioselectivities (93–>99%).

  在水和四丁基溴化铵存在下，开发出了高对映选择性的 L-硫代氨酸催化δ-氨氧基化醛，然后进行原位诱导，得到相应的δ-氨氧基醇，收率从好到高（74%-88%），对映选择性极佳（93%->99%）。
• The Direct and Enantioselective Organocatalytic α-Oxidation of Aldehydes
  作者：Sean P. Brown、Michael P. Brochu、Christopher J. Sinz、David W. C. MacMillan

  DOI：10.1021/ja037096s

  日期：2003.9.1

  The first direct enantioselective catalytic alpha-oxidation of carbonyls has been accomplished. The use of enamine catalysis has provided a new organocatalytic strategy for the enantioselective oxyamination of aldehydes, to generate alpha-oxyaldehydes, important chiral synthons for natural product and medicinal agent synthesis. The use of l-proline as the asymmetric catalyst has been found to mediate the oxidation of a large variety of aldehyde substrates with nitrosobenzene serving as the electrophilic oxidant. A diverse spectrum of aldehyde substrates can also be accommodated in this new organocatalytic transformation. While catalyst quantities of 2 mol % were generally employed in this study, successful oxidations conducted using catalyst loadings as low as 0.5 mol % are described.