(R)-ethyl 2-hydroxy-2-(thiophen-2-yl)acetate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: (R)-ethyl 2-hydroxy-2-(thiophen-2-yl)acetate
• 英文别名: ethyl (2R)-2-hydroxy-2-thiophen-2-ylacetate
• 化学式: C₈H₁₀O₃S
• 分子量: 186.232
• InChiKey: BDYPNJQVKHKGPQ-ZETCQYMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  74.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-噻酚乙酯乙酸乙酯 在 二甲基苯基硅烷 、 C₅₂H₅₄ 、 三环己基膦 、 bis(pentafluorophenyl)borane 、 氟化氢吡啶 作用下， 以 甲苯 、 正己烷 为溶剂， 反应 5.5h， 以87%的产率得到(R)-ethyl 2-hydroxy-2-(thiophen-2-yl)acetate
  参考文献：
  名称：

  手性受阻路易斯对催化 1,2-二羰基化合物的高度对映选择性氢化硅烷化

  摘要：

  利用三环己基膦和从二炔原位衍生的手性烯基硼烷的组合作为受挫的路易斯对催化剂，首次成功实现了 1,2-二羰基化合物的高度对映选择性氢化硅烷化。以 52-98% 的收率和 86-99% 的 ee's 获得了多种光学活性 α-羟基酮和酯。

  DOI：

  10.1021/jacs.5b13104

文献信息

• Novel diphosphines, their complexes with transisition metals and their use in asymmetric synthesis
  申请人：——

  公开号：US20040260101A1

  公开（公告）日：2004-12-23

  The invention relates to novel diphosphines, in optically pure or racemic form, of formula (I): 1 in which: R 1 and R 2 are a (C 5 -C 7 )cycloalkyl group, an optionally substituted phenyl group or a 5-membered heteroaryl group; and A is (CH 2 —CH 2 ) or CF 2 . The invention further relates to the use of a compound of formula (I) as a ligand for the preparation of a metal complex useful as a chiral catalyst in asymmetric catalysis, and to the chiral metal catalysts comprising at least one ligand of formula (I).

  该发明涉及一种新型二膦化合物，其为光学纯或外消旋形式，化学式（I）如下： 其中： R1和R2为(C5-C7)环烷基，可选择取代的苯基或5-成员杂环烷基；以及 A为(CH2-CH2)或CF2。 该发明还涉及将化合物的化学式（I）用作配体，用于制备金属配合物，该金属配合物在不对称催化中作为手性催化剂有用，并且包括至少一个化学式（I）的手性金属催化剂。
• Synthesis and Molecular Modeling Studies of SYNPHOS, a New, Efficient Diphosphane Ligand For Ruthenium-Catalyzed Asymmetric Hydrogenation
  作者：Sébastien Duprat de Paule、Séverine Jeulin、Virginie Ratovelomanana-Vidal、Jean-Pierre Genêt、Nicolas Champion、Philippe Dellis

  DOI：10.1002/ejoc.200200634

  日期：2003.5

  A new, optically active, atropisomeric diphosphane ligand, (2,3,2′,3′-tetrahydro-5,5′-bi(1,4-benzodioxin)-6,6′-diyl)bis-(diphenylphosphane) (SYNPHOS®), has been synthesized, characterized, and used in ruthenium-catalyzed asymmetric hydrogenations. This new ligand has been compared with other atropisomeric diphosphanes (BINAP and MeO-BIPHEP) with respect to their dihedral angles calculated by molecular

  一种新的光学活性阻转异构二膦配体，(2,3,2',3'-四氢-5,5'-bi(1,4-benzodioxin)-6,6'-diyl)bis-(diphenylphosphane) ( SYNPHOS®)，已被合成、表征并用于钌催化的不对称氢化。这种新配体已与其他阻转异构二膦（BINAP 和 MeO-BIPHEP）在分子模型计算的二面角和钌介导的氢化反应的对映选择性方面进行了比较。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Enantioselective Friedel-Crafts Alkylation of Thiophenes with Ethyl Glyoxylate: Easy Access to Chiral Secondary Alcohols
  作者：Zhong Huang、Jingchang Zhang、Yuqiang Zhou、Nai-Xing Wang

  DOI：10.1002/ejoc.201001455

  日期：2011.2

  Friedel–Crafts alkylation reactions of ethyl glyoxylate with various thiophenes to give the corresponding chiral secondary alcohols were demonstrated. The majority of these reactions proceeded with good enantioselectivities (up to 91 %) and satisfactory isolated yields. Notably, we found that 2-substituted thiophenes underwent the reaction more smoothly than unsubstituted and 3-substituted thiophenes

  乙醛酸乙酯与各种噻吩的 Friedel-Crafts 烷基化反应得到了相应的手性仲醇。大多数这些反应以良好的对映选择性（高达 91%）和令人满意的分离产率进行。值得注意的是，我们发现 2-取代的噻吩比未取代和 3-取代的噻吩反应更顺利。
• Synthesis and use of chiral substituted benzenes containing 1,2-diols protected as cyclic acetals
  作者：Chandrashekar Ramarao、Ramadevi Nandipati、Rajasekhar Navakoti、Ramanjaneyulu Kottamasu

  DOI：10.1016/j.tetlet.2011.11.111

  日期：2012.2

  diacetals using 2,3-butane dione. These diacetals are extremely robust and can be further chemically diversified and resolved with chirality embedded in the 1,4-dioxane ring attached to the aromatic back bone as a result of the anomeric effect. These systems can serve as ligands, auxiliaries or organocatalysts for asymmetric synthesis.

  1,3-二羟基苯已被2,3-丁烷二酮保护为环状二缩醛。这些二缩醛非常结实，由于异头作用，其手性可嵌入与芳香族背骨相连的1,4-二恶烷环中，并且可以进一步化学多样化和拆分。这些体系可以用作不对称合成的配体，助剂或有机催化剂。
• 10.1016/j.tet.2024.134068
  作者：Sosunovych, Bohdan S.、Timokhin, Oleksii S.、Kucher, Olexandr V.、Demianyk, Nadiia Y.、Hys, Denys V.、Zvarych, Yelyzaveta A.、Smolii, Oleg B.、Vashchenko, Bohdan V.、Grygorenko, Oleksandr O.

  DOI：10.1016/j.tet.2024.134068

  日期：——

  Synthesis and enzymatic resolution of a new class of alicyclic and heterocyclic mandelic acid derivatives was described. The method relied on the preparation of cyanohydrins from the commercially available aldehydes followed by hydrolysis to corresponding racemic hydroxy esters that were used in the resolution with the enzyme. An alternative approach was proposed for compounds that were not suitable

  描述了一类新型脂环族和杂环扁桃酸衍生物的合成和酶促拆分。该方法依赖于从市售醛制备氰醇，然后水解成相应的外消旋羟基酯，用于用酶进行拆分。对于不适合此程序的化合物提出了替代方法。对于选定的实施例，使用随后的酯水解、随后非对映体盐的对映体富集重结晶来合成相应的扁桃酸类似物。