methyl (2S,3S)-2-chloro-3-hydroxy-3-phenylpropanoate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: methyl (2S,3S)-2-chloro-3-hydroxy-3-phenylpropanoate
• 化学式: C₁₀H₁₁ClO₃
• 分子量: 214.649
• InChiKey: OXWHLUNHUCVJKF-IUCAKERBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  methyl (2Z)-3-phenylprop-2-enoate 在 氯 作用下， 以 甲醇 为溶剂， 反应 5.0h， 生成 methyl (2S,3S)-2-chloro-3-hydroxy-3-phenylpropanoate
  参考文献：
  名称：

  Lasne,M.-C. et al., Bulletin de la Societe Chimique de France, 1973, p. 1751 - 1756

  摘要：

  DOI：

文献信息

• The vicinal functionalization of olefins: a facile route to the direct synthesis of β-chlorohydrins and β-chloroethers
  作者：Peraka Swamy、Macharla Arun Kumar、Marri Mahender Reddy、Mameda Naresh、Kodumuri Srujana、Nama Narender

  DOI：10.1039/c4ra01641f

  日期：——

  An efficient and environmentally benign protocol for the synthesis of vicinal chlorohydroxy and chloromethoxy derivatives in a highly regioselective manner from olefins using NH4Cl as a chlorine source and oxone as an oxidant in aqueous acetone and methanol is demonstrated. This methodology offers an additive and metal chloride free approach and is endowed with simple reaction conditions, high yields

  证明了在丙酮和甲醇水溶液中，以NH 4 Cl为氯源，以oxone为氧化剂从烯烃以高度区域选择性的方式合成邻位氯羟基和氯甲氧基衍生物的有效且环境友好的方案。该方法提供了无添加剂和无金属氯化物的方法，并具有简单的反应条件，高收率，广泛的底物范围和良好的官能团耐受性。而且，具有末端双键的芳族底物仅表现出马尔可夫尼科夫选择性，而内部烯烃显示出排他性区域控制和低至中等的非对映选择性。
• Highly regio- and diastereoselective halohydroxylation of olefins: a facile synthesis of vicinal halohydrins
  作者：Jinglei Zhang、Jie Wang、Zhuibai Qiu、Yang Wang

  DOI：10.1016/j.tet.2011.06.077

  日期：2011.9

  out under mild conditions in the presence of N-tosyl-l-threonine (NTsLT) as an acidic additive using chloramine T trihydrate, 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) or N-bromoacetamide (AcNHBr) as the halogen source, respectively, affording the corresponding vicinal halohydrins in good to high yields with excellent regio- and stereoselectivities.

  基于各种具有给电子或吸电子取代基的烯烃的直接卤代羟基化，已经开发了一种用于合成邻位氯醇或溴代醇衍生物的有效方法。该反应在温和条件下在的存在下进行Ñ甲苯磺酰升-苏氨酸（NTsLT）作为酸性添加剂使用氯胺-T三水合物，1,3-二氯-5,5-二甲基（DCDMH）或ñ -bromoacetamide（ AcNHBr）作为卤素源，分别以高至高收率提供相应的邻位卤代醇，并具有出色的区域选择性和立体选择性。
• Biocatalytic dynamic reductive kinetic resolution of aryl α-chloro β-keto esters: divergent, stereocontrolled synthesis of diltiazem, clentiazem, and siratiazem
  作者：Xiaoping Yue、Yitong Li、Minjie Liu、Di Sang、Zedu Huang、Fener Chen

  DOI：10.1039/d2cc03102g

  日期：——

  of 100 g L−1 of substrate 6b at a ten-gram scale was achieved with a continuous fed-batch strategy, affording anti-(2S,3S)-1b, the key intermediate of diltiazem, in a record-breaking space-time yield of 96 g L−1 d−1. An eight-step synthesis of diltiazem, clentiazem, and siratiazem was accomplished in 32–45% overall yields, featuring this versatile biocatalytic reduction reaction as well as an efficient

  对芳基 α-氯 β-酮酯进行酮还原酶 (KRED) 催化的动态还原动力学拆分 (DYRKR) 的首次系统研究，并在 74– 98% 的分离产率，以及中等至优异的非对映选择性（高达 >99 : 1 dr）和良好至优异的对映选择性（大部分 >99% ee）。LfSDR1 催化完全还原 10 克规模的 100 g L -1底物6b是通过连续补料分批策略实现的，在破纪录的时空产量 96 g L -1 d -1. 地尔硫卓、克林特西姆和西拉硫卓的八步合成以 32-45% 的总收率完成，具有这种多功能的生物催化还原反应以及高效、绿色的流动氯化反应。
• Enantioselective ruthenium-mediated hydrogenation: developments and applications
  作者：Virginie Ratovelomanana-Vidal、Jean-Pierre Genêt

  DOI：10.1016/s0022-328x(98)00680-9

  日期：1998.9

  A general preparation of chiral ruthenium(II) catalysts and the homogeneous enantioselective hydrogenation of prochiral olefins and keto groups are presented. Some applications to the synthesis of biologically active compounds are reported. (C) 1998 Elsevier Science S.A. All rights reserved.
• Dynamic kinetic resolution of α-chloro β-keto esters and phosphonates: hemisynthesis of Taxotere® through Ru-DIFLUORPHOS asymmetric hydrogenation
  作者：Sébastien Prévost、Sébastien Gauthier、Maria Cristina Caño de Andrade、Céline Mordant、Ali Rhida Touati、Philippe Lesot、Philippe Savignac、Tahar Ayad、Phannarath Phansavath、Virginie Ratovelomanana-Vidal、Jean-Pierre Genêt

  DOI：10.1016/j.tetasy.2010.05.017

  日期：2010.6

  The dynamic kinetic resolution (DKR) of racemic alpha-chloro beta-ketoesters and alpha-chloro beta-ketophosphonates through ruthenium-mediated asymmetric hydrogenation is reported. The corresponding alpha-chloro beta-hydroxyesters and alpha-chloro beta-hydroxyphosphonates were obtained in good to high enantio- and diastereomeric excesses using, in particular, the atropisomeric ligand DIFLUORPHOS. This methodology allowed an efficient preparation of the anti phenylisoserine side chain of Taxotere (R) which has been used for the hemisynthesis of the cancer therapeutic agent itself. In addition, C-13 NMR in chiral oriented solvents was used to investigate the DKR effect. (C) 2010 Elsevier Ltd. All rights reserved.