methyl (+/-)-(2R,3R)-2-bromo-3-methoxy-3-phenylpropanoate | 52742-05-9

• 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: methyl (+/-)-(2R,3R)-2-bromo-3-methoxy-3-phenylpropanoate
• 英文别名: erythro-methyl-2-bromo-3-methoxy-3-phenylpropionate；methyl 2-bromo-3-methoxy-3-phenylpropanoate；(2RS,3RS)-2-bromo-3-methoxy-3-phenyl-propionic acid methyl ester；(2RS,3RS)-2-Brom-3-methoxy-3-phenyl-propionsaeure-methylester；methyl (2S,3S)-2-bromo-3-methoxy-3-phenylpropanoate
• CAS: 52742-05-9；52781-50-7；60456-13-5；64856-34-4；65091-58-9
• 化学式: C₁₁H₁₃BrO₃
• 分子量: 273.126
• InChiKey: KOMNPVFCQMJEHR-UWVGGRQHSA-N

物化性质

• 熔点：
  74-76 °C
• 沸点：
  327.3±37.0 °C(Predicted)
• 密度：
  1.394±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (+/-)-(2R,3R)-2-bromo-3-methoxy-3-phenylpropanoate 在 偶氮二异丁腈 、 氘代三正丁基锡 作用下， 以83%的产率得到methyl 3-methoxy-3-phenylpropanoate-2-d
  参考文献：
  名称：

  Stereoselective hydrogen-transfer reactions involving acyclic radicals. A study of radical conformations using semiempirical calculations

  摘要：

  DOI：

  10.1021/ja00038a072
• 作为产物：
  描述：

  Methyl cinnamate 在 甲醇 、 溴 、 lead(II) oxide 作用下， 生成 methyl (+/-)-(2R,3R)-2-bromo-3-methoxy-3-phenylpropanoate
  参考文献：
  名称：

  Kollonitsch et al., Acta Chimica Academiae Scientiarum Hungaricae, 1955, vol. 5, p. 13,20

  摘要：

  DOI：

文献信息

• Comparative study of the vicinal functionalization of olefins with 2:1 bromide/bromate and iodide/iodate reagents
  作者：Manoj K. Agrawal、Subbarayappa Adimurthy、Bishwajit Ganguly、Pushpito K. Ghosh

  DOI：10.1016/j.tet.2009.01.095

  日期：2009.4

  halohydrins, halo methyl ethers, and halo acetates from olefins using 2:1 Br−/BrO3− and I−/IO3− reagents. In many cases both reagents afforded products selectively in high yields. The highest halogen atom efficiencies attained were 97% and 93% for Br−/BrO3− and I−/IO3−, respectively. Of the two reagents, I−/IO3− was established to be the preferred reagent for vicinal functionalization of linear alkenes and

  比较评价在邻位卤代醇，卤代甲基醚和卤代乙酸盐的合成由从使用2-烯烃：1溴- /的BrO 3 -和我- / IO 3 -试剂。在许多情况下，两种试剂都以高收率选择性地提供产物。得到最高卤素原子效率为97％和溴93％- /的BrO 3 -和我- / IO 3 - ，分别。这两个试剂，我- / IO 3 -已确定“丙烯酰胺”是用于直链烯烃的邻位官能化以及用于制备卤代乙酸酯的优选试剂。然而，只有溴- /的BrO 3 -是有效的邻位官能反式-二苯乙烯和查耳酮。
• NaIO₄-Mediated Selective Oxidative Halogenation of Alkenes and Aromatics Using Alkali Metal Halides
  作者：Gajanan K. Dewkar、Srinivasarao V. Narina、Arumugam Sudalai

  DOI：10.1021/ol0358206

  日期：2003.11.1

  [reaction: see text] NaIO(4) oxidizes alkali metal halides efficiently in aqueous medium to halogenate alkenes and aromatics and produce the corresponding halo derivatives in excellent regio and stereoselectivity. The system also demonstrates the asymmetric version of bromo hydroxylation using beta-cyclodextrin complexes, resulting in moderate ee.

  [反应：见正文] NaIO（4）在水性介质中有效氧化碱金属卤化物，以卤化烯烃和芳烃，并以极好的区域和立体选择性产生相应的卤代衍生物。该系统还证明了使用β-环糊精络合物的溴羟基化反应的不对称形式，可产生适度的ee。
• Organocatalysis in the stereoselective bromohydrin reaction of alkenes
  作者：Sukanta Bar

  DOI：10.1139/v10-053

  日期：2010.7

  An efficient regio- and stereo-selective (>99:1) trans-bromohydrination (bromohydroxylation and bromomethoxylation) of alkenes including α,β-unsaturated carbonyl compounds with N-bromosuccinimide (NBS) has been achieved by using 1.0 mol% of N,N′-diarylthiourea catalyst.

  通过使用 1.0 mol%的 N,N′-二基硫脲催化剂，实现了烯烃（包括 α、β-不饱和羰基化合物）与 N-溴代琥珀酰亚胺（NBS）的高效区域和立体选择性（99:1）反式溴水化反应（溴羟化反应和溴甲氧基化反应）。
• A Simple and Efficient Method for Regioselective and Stereoselective Synthesis of Vicinal Bromohydrins and Alkoxybromides from an Olefin
  作者：Prodeep Phukan、Pranita Chakraborty、Dolly Kataki

  DOI：10.1021/jo0600611

  日期：2006.9.1

  very rapid and efficient method has been developed for the synthesis of vicinal bromohydrins and alkoxybromides directly from an olefin without any catalyst. The reaction was performed in CH3CN−water (4:1) or alcohol using N,N-dibromo-p-toluenesulfonamide (TsNBr2) as the brominating agent. Excellent yields and regio- and stereoselectivities have been obtained. Bromohydrins are formed instantaneously

  已经开发了非常快速有效的方法，用于直接从烯烃合成邻位溴代醇和烷氧基溴化物，而无需任何催化剂。反应是在CH 3 CN-水（4：1）或酒精中，使用N，N-二溴-对甲苯甲苯磺酰胺（TsNBr 2）作为溴化剂进行的。已经获得了优异的产率以及区域选择性和立体选择性。溴代醇是瞬间形成的，而烷氧基溴化物的形成则需要30-60分钟。
• The Use of Lewis Acids in Radical Chemistry. Chelation-Controlled Radical Reductions of Substituted α-Bromo-β-alkoxy Esters and Chelation-Controlled Radical Addition Reactions
  作者：Yvan Guindon、J. Rancourt

  DOI：10.1021/jo980636x

  日期：1998.9.1

  The radical reduction of a series of alpha-bromo-beta-alkoxy esters under chelation-controlled conditions is reported. Proceeding with high stereoselectivity in the presence of MgBr2. OEt2, reductions give access to syn, products. Systematic variations in substrate substituents show that these reactions tolerate a wide variety of alkyl functionalities at positions 2 and 3 and are relatively unaffected by the nature of the ester group. Changes to the alkoxy function indicate that a bidentate chelate is involved in the reaction and that an excess of MgBr2. OEt2 is required for optimum selectivity by favoring this species in preference to the anti-selective monodentate or nonchelated pathways. Competition experiments suggest that the monodentate pathway is kinetically favored over the bidentate one. The suppressibility of the reaction by radical chain inhibitors and the need for initiation indicate the intermediacy of radicals. Further support for this mechanism includes both radical addition to alpha,beta-unsaturated esters and reduction of bromides conducted in the presence of a Lewis acid.