tert-butyl 3-hydroxy-2-methyl-3-phenylpropionate | 72658-21-0

• 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 3-hydroxy-2-methyl-3-phenylpropionate
• 英文别名: tert-butyl (2S,3R)-3-hydroxy-2-methyl-3-phenylpropanoate
• CAS: 72658-21-0
• 化学式: C₁₄H₂₀O₃
• 分子量: 236.311
• InChiKey: JYUCJWFNNCSFPX-CMPLNLGQSA-N

物化性质

• 沸点：
  341.5±22.0 °C(predicted)
• 密度：
  1.057±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  tert-butyl 3-hydroxy-2-methyl-3-phenylpropionate 、 碘化钠 、 三甲基氯硅烷 以79%的产率得到
  参考文献：
  名称：

  MATTESON, DONALD S.;MICHNICK, JOHN T., ORGANOMETALLICS, 9,(1990) N2, C. 3171-3177

  摘要：

  DOI：
• 作为产物：
  描述：

  2-甲基-3-羟基-3-苯基丙酸叔丁酯 在 Jones’ reagent 、 tetrabutylammonium borohydride 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 6.0h， 生成 tert-butyl 3-hydroxy-2-methyl-3-phenylpropionate
  参考文献：
  名称：

  氯化锰（II）或四丁基硼氢化铵催化的硼氢化钠立体选择性还原2-甲基-3-氧代酯（或酰胺）。实用的赤型和苏型-3-羟基-2-甲基酯（或酰胺）的制备方法

  摘要：

  赤-3-羟基-2- methylpropionates或赤-3-羟基-2-甲基丙酰胺用高立体选择性加入NaBH制备4减少在相应的2-甲基-3-氧代酯或2-甲基-3-氧代酰胺的催化量的氯化锰（II）的存在。另一方面，用n -Bu 4 NBH 4还原这些底物选择性地提供了苏式异构体。还描述了在1N HCl-MeOH中用NaBH 3 CN对2-甲基-3-氧代酰胺的赤型选择性还原。

  DOI：

  10.1016/s0040-4020(01)81804-4

文献信息

• Lewis Base Activation of Lewis Acids:  Catalytic, Enantioselective Addition of Silyl Ketene Acetals to Aldehydes
  作者：Scott E. Denmark、Gregory L. Beutner、Thomas Wynn、Martin D. Eastgate

  DOI：10.1021/ja047339w

  日期：2005.3.1

  The concept of Lewis base activation of Lewis acids has been reduced to practice for catalysis of the aldol reaction of silyl ketene acetals and silyl dienol ethers with aldehydes. The weakly acidic species, silicon tetrachloride (SiCl4), can be activated by binding of a strongly Lewis basic chiral phosphoramide, leading to in situ formation of a chiral Lewis acid. This species has proven to be a competent

  路易斯酸的路易斯碱活化的概念已被简化用于催化甲硅烷基乙烯酮缩醛和甲硅烷基二烯醇醚与醛的羟醛反应。弱酸性物质四氯化硅 (SiCl4) 可以通过结合强路易斯碱性手性磷酰胺而被激活，导致手性路易斯酸的原位形成。该物质已被证明是将乙酸酯、丙酸酯和异丁酸酯衍生的甲硅烷基乙烯酮缩醛与共轭和非共轭醛进行羟醛加成反应的有效催化剂。此外，还证明了甲硅烷基二烯醇醚的乙烯基羟醛反应。高水平的区域-，抗非对映-，
• Enantioselective Aldol and Michael Additions of Achiral Enolates in the Presence of Chiral Lithium Amides and Amines
  作者：Eusebio Juaristi、Albert K. Beck、Jesper Hansen、Thomas Matt、Triptikumar Mukhopadhyay、Malgorzata Simson、Dieter Seebach

  DOI：10.1055/s-1993-26041

  日期：——

  It is now well established that lithium enolates and analogous derivatives generally exist as complex structures held together by noncovalent bonds ("supramolecules"). In particular, Li enolates aggregate to give dimers, tetramers, and higher oligomers, whose metal centers may be complexed by solvent molecules or chelating ligands. In addition, the anionoid part of the enolates may hydrogen-bond to weak acids such as secondary amines. Furthermore, such supramolecules can be product-forming species in synthetic reactions of Li enolates. This paper describes our observations of the temporary incorporation of chiral amines or chiral lithium amides into achiral lithium enolate aggregates (an interaction which is simply broken during aqueous workup!) to give enantiomerically enriched products. In particular, enantioselective aldol and Michael additions between achiral enolates and achiral aldehydes or achiral nitroolefins have been achieved in the presence of several chiral amines (or their lithium amides) derived from (S)-valine or (R,R)-tartaric acid. Finally, this report demonstrates the potential usefulness in asymmetric synthesis of ortho lithiation directed by chiral α-aminoalkoxides.

  目前已经充分确定，锂烯醇盐及其类似衍生物通常以非共价键结合而成的复杂结构（“超分子”）存在。特别是，锂烯醇盐聚集形成二聚体、四聚体和高阶寡聚体，其金属中心可能被溶剂分子或螯合配体络合。此外，烯醇盐的阴离子部分可能与二级胺等弱酸形成氢键。而且，这些超分子在锂烯醇盐的合成反应中可能是产物形成物种。本文描述了我们观察到的将手性胺或手性锂酰胺暂时掺入非手性锂烯醇盐聚集体（在水中处理时这种相互作用被简单破坏！）从而产生手性富集产物的现象。特别是，在几种由(S)-缬氨酸或(R,R)-酒石酸衍生的手性胺（或它们的锂酰胺）存在下，实现了非手性烯醇盐与非手性的醛或非手性硝基烯烃的立体选择性羟醛缩合反应和迈克尔加成反应。最后，本报告展示了手性α-氨基烷氧基导向的邻位锂化在对映选择性合成中的潜在应用价值。
• A mild aldol reaction of aryl aldehydes through palladium-catalyzed hydrosilation of α,β-unsaturated carbonyl compounds with trichlorosilane
  作者：Syun-ichi Kiyooka、Atsushi Shimizu、Seiko Torii

  DOI：10.1016/s0040-4039(98)01030-2

  日期：1998.7

  A mild aldol reaction of aryl aldehydes took place by using N,N-dimethylacrylamide and trichlorosilane with a catalytic amount of tetrakis(triphenyl-phosphine)palladium. a unique anti selectivity was observed in the reaction.

  通过使用N，N-二甲基丙烯酰胺和三氯硅烷与催化量的四（三苯基膦）钯进行芳基醛的温和的醛醇缩合反应。在反应中观察到独特的抗选择性。
• Rhenium-catalyzed reaction of carbonyl compounds with ketene silyl acetals
  作者：Yutaka Nishiyama、Kenta Kaiba、Rui Umeda

  DOI：10.1016/j.tetlet.2009.11.109

  日期：2010.2

  It was found that rhenium complex is an effective catalyst for the reaction of carbonyl compounds with ketene silyl acetals. A wide range of β-silyloxy esters is obtained by the treatment of carbonyl compounds with ketene silyl acetals in the presence of a catalytic amount of ReBr(CO)5 in moderate to good yields.

  发现rh络合物是羰基化合物与乙烯酮甲硅烷基缩醛反应的有效催化剂。在催化量的ReBr（CO）5存在下，通过用乙烯酮甲硅烷基缩醛处理羰基化合物，可以以中等至良好的收率获得大量的β-甲硅烷氧基酯。
• High Performance of Rh(Phebox) Catalysts in Asymmetric Reductive Aldol Reaction:  High Anti-Selectivity
  作者：Hisao Nishiyama、Takushi Shiomi、Yasunori Tsuchiya、Isamu Matsuda

  DOI：10.1021/ja050698m

  日期：2005.5.1

  Chiral rhodium(bisoxazolinylphenyl) complexes (1 mol %) efficiently catalyze the asymmetric reductive aldol reaction of aldehydes and alpha,beta-unsaturated esters at 50 degrees C for ca. 0.5-1.0 h with several hydrosilanes to give the corresponding beta-hydroxypropionates with extremely high anti-selectivity (up to 98%) and enantioselectivity (up to 96% ee). The stereochemical outcome is likely due

  手性铑(双恶唑啉基苯基) 配合物 (1 mol %) 有效地催化醛和 α，β-不饱和酯在 50 摄氏度的不对称还原醛醇反应约。使用几种氢硅烷反应 0.5-1.0 小时，得到具有极高抗选择性（高达 98%）和对映选择性（高达 96% ee）的相应 β-羟基丙酸酯。立体化学结果可能是由于涉及铑-(E)-烯醇化物的椅子状循环过渡态。