(R)-Methyl 4-benzyloxy-3-hydroxybutanoate | 114784-19-9

• 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: (R)-Methyl 4-benzyloxy-3-hydroxybutanoate
• 英文别名: methyl (R)-4-benzyloxy-3-hydroxybutanoate；methyl (R)-4-benzyloxy-3-hydroxybutyrate；(R)-4-benzyloxy-3-hydroxybutanoic acid methyl ester；methyl (3R)-3-hydroxy-4-phenylmethoxybutanoate
• CAS: 114784-19-9
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: CCZLIOHIMSFAIF-LLVKDONJSA-N

物化性质

• 沸点：
  350.0±32.0 °C(Predicted)
• 密度：
  1.144±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-Methyl 4-benzyloxy-3-hydroxybutanoate 在 sodium tetrahydroborate 、 三乙基硼 、 4-甲基苯磺酸吡啶 、 lithium diisopropyl amide 作用下， 以 甲苯 为溶剂， 反应 11.75h， 生成 (R)-6-Benzyloxymethyl-5,6-dihydro-2-pyrone
  参考文献：
  名称：

  Asymmetric hydrogenation of 3,5-Dioxoesters catalyzed by Ru-binap complex: A short step asymmetric synthesis of 6-substituted 5,6-dihydro-2-pyrones

  摘要：

  Asymmetric hydrogenation of 3,5-dioxoesters 1a-c using Ru2Cl4((R) or (S)-binap)2(NEt3) as the catalyst gave dominantly anti 3,5-dihydroxyesters 2, which were then converted into unsaturated lactones 5a-b (ca. 80% e.e.). The pathway of the hydrogenation reaction was also investigated by asymmetric hydrogenation of (R)- or (S)-5-hydroxy-3-oxoesters 8a-c. It was revealed that the Ru-binap catalyzed hydrogenation of 1a-b proceed dominantly via the beta-diketone mode. A convenient asymmetric synthesis of hydroxylactone 3c and unsaturated lactone 5c was presented.

  DOI：

  10.1016/s0040-4020(01)86300-6
• 作为产物：
  描述：

  叔丁基3-氧代-(苯甲氧基)-丁酸 在 Ru₂Cl₄-(S)-(2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)2*NEt₃ 硫酸 、 氢气 作用下， 以 甲醇 为溶剂， 30.0 ℃ 、10.13 MPa 条件下， 生成 (R)-Methyl 4-benzyloxy-3-hydroxybutanoate
  参考文献：
  名称：

  Asymmetric hydrogenation of 3,5-Dioxoesters catalyzed by Ru-binap complex: A short step asymmetric synthesis of 6-substituted 5,6-dihydro-2-pyrones

  摘要：

  Asymmetric hydrogenation of 3,5-dioxoesters 1a-c using Ru2Cl4((R) or (S)-binap)2(NEt3) as the catalyst gave dominantly anti 3,5-dihydroxyesters 2, which were then converted into unsaturated lactones 5a-b (ca. 80% e.e.). The pathway of the hydrogenation reaction was also investigated by asymmetric hydrogenation of (R)- or (S)-5-hydroxy-3-oxoesters 8a-c. It was revealed that the Ru-binap catalyzed hydrogenation of 1a-b proceed dominantly via the beta-diketone mode. A convenient asymmetric synthesis of hydroxylactone 3c and unsaturated lactone 5c was presented.

  DOI：

  10.1016/s0040-4020(01)86300-6

文献信息

• A New Class of Tunable Dendritic Diphosphine Ligands: Synthesis and Applications in the Ru-Catalyzed Asymmetric Hydrogenation of Functionalized Ketones
  作者：Baode Ma、Tingting Miao、Yihua Sun、Yanmei He、Ji Liu、Yu Feng、Hui Chen、Qing-Hua Fan

  DOI：10.1002/chem.201402709

  日期：2014.8.4

  dendritic 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl (BINAP) ligands was prepared by attaching polyaryl ether dendrons onto the four phenyl rings on the P atoms. Their ruthenium complexes were employed in the asymmetric hydrogenation of β‐ketoesters, α‐ketoesters, and α‐ketoamides to reveal the effects of dendron size on the catalytic properties. The second‐ and third‐generation catalysts exhibited excellent

  一系列可调的G 0 –G 3树枝状2,2'-双（二苯基膦基）-1,1'-联萘（BINAP）配体是通过将聚芳基醚树枝状分子连接到P原子上的四个苯环上而制备的。他们的钌配合物用于β-酮酸酯，α-酮酸酯和α-酮酰胺的不对称氢化反应，揭示了树枝状分子大小对催化性能的影响。第二代和第三代催化剂表现出优异的对映选择性，明显高于从小分子催化剂和第一代催化剂获得的对映选择性。分子模型表明，大的树枝状楔形物的结合会影响金属中心周围的空间环境。此外，
• An Improved Asymmetric Reformatsky Reaction Mediated by (−)-<i>N</i>,<i>N</i>-Dimethylaminoisoborneol
  作者：Ralf J. Kloetzing、Tobias Thaler、Paul Knochel

  DOI：10.1021/ol0531381

  日期：2006.3.1

  (-)-N,N-Dimethylaminoisoborneol ((-)-DAIB) was found to be an excellent ligand for the enantioselective addition of Reformatsky reagents to aromatic and aliphatic aldehydes. Enantioselectivities up to 93% ee were obtained with sulfur-containing aldehydes.

  (-)-N,N-二甲基氨基异薄荷醇 ((-)-DAIB) 被发现是一种非常适合用于芳香族和脂肪族醛与Reformatsky 试剂进行手性选择性加成的配体。使用含硫的醛类时，获得了高达93% ee的手性选择性效果。
• Process for producing ß-hydroxyester
  申请人：Igi Kimitaka

  公开号：US20060122419A1

  公开（公告）日：2006-06-08

  A process for producing a β-hydroxyester by reacting an epoxide, an alcohol and carbon monoxide in the presence of a cobalt carbonyl compound as catalyst, which is characterized in using as co-catalyst, a pyridine derivative having an amino substituent of formula (1), wherein R 1 and R 2 are independently hydrogen, formyl, acyl, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or R 1 and R 2 may be taken together with the adjacent nitrogen atom to form a ring, and n is an integer of 1 or 2.

  一种生产β-羟基酯的方法，包括在钴羰基化合物的催化下，通过反应环氧化物、醇和一氧化碳来实现，其特征在于使用一种具有式（1）中氨基取代基的吡啶衍生物作为共催化剂，其中R1和R2独立地是氢、甲酰、酰基、烷氧基羰基、取代或未取代的烷基、取代或未取代的芳基烷基、取代或未取代的芳基，或R1和R2可以与相邻的氮原子一起形成环，n是1或2的整数。
• Process for producing β-hydroxyester
  申请人：Daiso Co., Ltd.

  公开号：US07256305B2

  公开（公告）日：2007-08-14

  A process for producing a β-hydroxyester by reacting an epoxide, an alcohol and carbon monoxide in the presence of a cobalt carbonyl compound as catalyst, which is characterized in using as co-catalyst, a pyridine derivative having an amino substituent of formula (1), wherein R1 and R2 are independently hydrogen, formyl, acyl, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or R1 and R2 may be taken together with the adjacent nitrogen atom to form a ring, and n is an integer of 1 or 2.

  一种生产β-羟酸酯的方法，通过在钴羰基化合物的催化下，反应环氧化物、醇和一氧化碳，并以具有式（1）中的含氨基取代基的吡啶衍生物作为辅助催化剂，其中R1和R2独立地为氢、甲酰基、酰基、烷氧基羰基、取代或未取代的烷基、取代或未取代的芳基烷基、取代或未取代的芳基，或R1和R2可以与相邻的氮原子结合形成环，n为1或2的整数。
• PROCESS FOR PRODUCING BETA-HYDROXYESTER
  申请人：DAISO CO., LTD.

  公开号：EP1616852B1

  公开（公告）日：2010-08-11