ethyl (2S,3R)-2-bromo-3-hydroxy-2-methyl-3-phenylpropionate | 285565-00-6

• 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: ethyl (2S,3R)-2-bromo-3-hydroxy-2-methyl-3-phenylpropionate
• 英文别名: ethyl (2S,3R)-2-bromo-3-hydroxy-2-methyl-3-phenylpropanoate
• CAS: 285565-00-6
• 化学式: C₁₂H₁₅BrO₃
• 分子量: 287.153
• InChiKey: BOQNABDKBHDWDE-PWSUYJOCSA-N

物化性质

• 沸点：
  370.6±37.0 °C(predicted)
• 密度：
  1.412±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (2S,3R)-2-bromo-3-hydroxy-2-methyl-3-phenylpropionate 在 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以75%的产率得到(1R,2R)-2-Bromo-2-methyl-1-phenyl-propane-1,3-diol
  参考文献：
  名称：

  Efficient enantio- and diastereoselective synthesis of enantiopure syn-α-bromo-β-hydroxy-α-methylpropionate esters and their cis-α,β-epoxy derivatives based on a chiral oxazaborolidinone-promoted asymmetric aldol reaction

  摘要：

  syn-alpha-Bromo-beta-hydroxy-alpha-methylpropionate esters were prepared in high diastereoselectivity with essentially enantiopure state by employing the chiral oxazaborolidinone-promoted asymmetric aldol reaction with beta-bromo-beta-methylketene silyl acetal. The subsequent subjection of the alpha-bromo-beta-hydroxy esters to basic conditions led to the quantitative transformation to the corresponding enantiopure cis-alpha,beta-epoxy derivatives, (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00089-6
• 作为产物：
  描述：

  ethyl 2-methylcinnamate 在 N-溴代丁二酰亚胺(NBS) 、 硫酸 、 水 作用下， 以 丙酮 为溶剂， 反应 12.0h， 生成 ethyl (2S,3R)-2-bromo-3-hydroxy-2-methyl-3-phenylpropionate 、 (2S,3S)-2-Bromo-3-hydroxy-2-methyl-3-phenyl-propionic acid ethyl ester
  参考文献：
  名称：

  Investigation of a model for 1,2-asymmetric induction in reactions of .alpha.-carbalkoxy radicals: a stereochemical comparison of reactions of .alpha.-carbalkoxy radicals and ester enolates

  摘要：

  The stereochemical course of reductions and allylations of alpha-carbalkoxy radicals with chiral centers at the beta-position are reported. Radicals without polar substituents, with alkoxyl or acetoxyl groups, and with hydroxyl groups at the beta-position were examined. Reactions showed selectivities ranging from low (50:50) to high (99:1). The results are discussed in terms of transition-state models that emphasize the importance of (1) allylic conformational analysis (minimization of A1,3 and A1,2 strain), (2) torisonal strain (minimization of eclipsed interactions), and (3) stereoelectronic effects.

  DOI：

  10.1021/jo00042a029

文献信息

• Diastereoselective radical debromination approach toward divergent syntheses of syn- and anti-propionate units, coupled with enantioselective and/or diastereoselective Lewis acid-promoted aldol reactions
  作者：Syun-ichi Kiyooka

  DOI：10.1016/j.tetasy.2003.06.005

  日期：2003.10

  methodology directed to the enantioselective synthesis of polypropionate backbones, available for the synthesis of polyketide natural products, has been developed by iterative enantio- and diastereoselective Lewis acid-promoted aldol reactions, followed by diastereoselective radical debromination reactions. A chiral oxazaborolidinone-promoted aldol reaction of a racemic aldehyde, derived from 2-methyl-1

  通过迭代对映和非对映选择性路易斯酸促进的醛醇缩合反应，然后进行非对映选择性自由基脱溴反应，已经开发出一种实用的方法学，该方法可用于合成聚酮化合物天然产物，可用于聚丙烯酸酯主链的对映选择性合成。由2-甲基-1,3-丙二醇衍生的外消旋醛与2-溴丙酸乙酯的甲硅烷基乙烯酮缩醛的手性草并氮杂硼硼烷酮促进的醛醇缩合反应导致相应的溴醛羟醛加合物的高度对映选择性形成，然后进行自由基脱溴与卜3 SNH在Et的存在3 B到发散给予顺式-和反-丙醛醇醛缩醛酸酯，是多用途的立体三联体。此外，还实现了丙酸酯单元的延长：手性顺式和反-α-甲基-β-保护的乙醛与甲硅烷基亲核试剂的BF 3 ·OEt 2促进的醛醇缩合反应以基本上完​​全的顺选择性进行。而TiCl 4促进的羟醛反应导致相当好的抗选择性。通过自由基还原将所得的溴代羟醛加合物发散地脱溴，得到完整的立体四线体。
• A Divergent Synthesis of Essentially Enantiopure<i>syn</i>- and<i>anti</i>-Propionate Aldol Adducts Based on the Chiral 1,3,2-Oxazaborolidin-5-one-Promoted Asymmetric Aldol Reaction Followed by Diastereoselective Radical Reduction
  作者：Syun-ichi Kiyooka、Kazi Abuds Shahid

  DOI：10.1246/bcsj.74.1485

  日期：2001.8

  Essentially, enantiopure syn- and anti-propionate aldol adducts were divergently synthesized using a novel strategy which utilizes both the highly enantioselective 1,3,2-oxazaborolidin-5-one-promoted aldol reaction with a ketene silyl acetal derived from ethyl 2-bromo propionate and a highly diastereoselective radical debromination reaction. These procedures provide yields that increase to a level

  本质上，对映纯的合成和反丙醇醛加合物是使用一种新的策略不同地合成的，该策略利用高度对映选择性的 1,3,2-oxazaborolidin-5-one-促进的醛醇反应与衍生自乙基 2-溴的乙烯酮甲硅烷基缩醛丙酸盐和高度非对映选择性的自由基脱溴反应。这些程序提供的产率增加到可用于实际合成的水平。
• Stereoselective Hydrogen Transfer Reactions Involving Acyclic Radicals. Tandem Substituted Tetrahydrofuran Formation and Stereoselective Reduction: Synthesis of the C17-C22 Subunit of Ionomycin
  作者：Y. Guindon、C. Yoakim、V. Gorys、W. W. Ogilvie、D. Delorme、J. Renaud、G. Robinson、J.-F. Lavallee、A. Slassi

  DOI：10.1021/jo00084a040

  日期：1994.3

  The tandem iodoetherification reaction and stereoselective reduction of acyclic radicals has been used in the stereocontrolled synthesis of substituted tetrahydrofurans. Such a tetrahydrofuran intermediate is regioselectively cleaved using Me(2)BBr to reveal the acyclic array 2 which represents the C-17-C-22 subunit of ionomycin. In experiments that provide for a better understanding of hydrogen transfer reactions involving acyclic radicals, a significant improvement in the stereoselectivity is observed when the two substituents at the stereogenic center alpha to the radical are imbedded in a cycle (''cycle effect''). A mechanistic rationale is discussed.
• A practical synthesis of essentially enantiopure syn-propionate aldols using a chiral oxazaborolidinone-promoted asymmetric aldol reaction coupled with radical reduction
  作者：Syun-ichi Kiyooka、Kazi A. Shahid、Mostofa A. Hena

  DOI：10.1016/s0040-4039(99)01278-2

  日期：1999.8

  Essentially enantiopure syn-propionate aldols (>98% ee) were prepared by a chiral oxazaborolidinone-promoted asymmetric aldol reaction, followed by a diastereoselective radical reduction with Bu3SnH and Et3B, which was carried out under chelation control. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Efficient enantio- and diastereoselective synthesis of enantiopure syn-α-bromo-β-hydroxy-α-methylpropionate esters and their cis-α,β-epoxy derivatives based on a chiral oxazaborolidinone-promoted asymmetric aldol reaction
  作者：Syun-ichi Kiyooka、Kazi A Shahid

  DOI：10.1016/s0957-4166(00)00089-6

  日期：2000.4

  syn-alpha-Bromo-beta-hydroxy-alpha-methylpropionate esters were prepared in high diastereoselectivity with essentially enantiopure state by employing the chiral oxazaborolidinone-promoted asymmetric aldol reaction with beta-bromo-beta-methylketene silyl acetal. The subsequent subjection of the alpha-bromo-beta-hydroxy esters to basic conditions led to the quantitative transformation to the corresponding enantiopure cis-alpha,beta-epoxy derivatives, (C) 2000 Elsevier Science Ltd. All rights reserved.