methyl (±)-anti-3-hydroxy-2-iodo-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 (±)-anti-3-hydroxy-2-iodo-3-phenylpropanoate
• 英文别名: methyl (2RS,3RS)-3-hydroxy-2-iodo-3-phenylpropanoate；erythro-methyl-3-hydroxy-2-iodo-3-phenylpropanoate；methyl (+/-)-3-hydroxy-2-iodo-3-phenylpropanoate；methyl anti-2-iodo-3-hydroxy-3-phenylpropanoate；methyl 3-hydroxy-2-iodo-3-phenylpropanoate；methyl (2S,3S)-3-hydroxy-2-iodo-3-phenylpropanoate
• 化学式: C₁₀H₁₁IO₃
• 分子量: 306.1
• InChiKey: FSEFURWCHKSGHN-IUCAKERBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 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

• 作为反应物：
  描述：

  methyl (±)-anti-3-hydroxy-2-iodo-3-phenylpropanoate 在 4-二甲氨基吡啶 、 phosphate buffer 、 lipase AS Amano 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 18.0h， 生成 (2R,3R)-methyl 3-hydroxy-2-iodo-3-phenylpropanoate
  参考文献：
  名称：

  Chemoenzymatic approach to optically active phenylglycidates: resolution of bromo- and iodohydrins

  摘要：

  Enantiomerically enriched phenylglycidates, precursors of the taxol C-13 phenylisoserine side chain and diltiazem. were prepared by kinetic resolution of anti-2-bromo-3-hydroxy- and anti-3-hydroxy-2-iodophenylpropanoates to provide enantioriched (2R,3R)- and (2S,3S)-halohydrins. The bulkiness and inflexibility of bromo and iodo groups in halohydrins have made them inaccessible to the active site of most of the lipases utilized for the hydrolysis of their acyloxy derivatives. In a set of 22 hydrolases screened herein, including native as well as commercial enzymes, only Aspergillus niger (Lipase AS, AMANO) could catalyze the hydrolysis with high enantioselectivity (E = 176). The resolved halohydrins easily underwent transformation to the corresponding (2S,3R)- and (2R,3S)phenylglycidates. (C) 26 E'lsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.08.026
• 作为产物：
  描述：

  Methyl cinnamate 在 N-碘代糖精 、 水 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以89%的产率得到methyl (±)-anti-3-hydroxy-2-iodo-3-phenylpropanoate
  参考文献：
  名称：

  使用 N-溴和 N-碘糖精从失活烯烃合成溴和碘醇

  摘要：

  N-溴和 N-碘糖精在水性有机溶剂中与缺电子烯烃如 α,β-不饱和酮、酸、酯和腈反应，以良好的收率生成相应的卤代醇。反应在室温下进行，大部分反应时间短且具有高抗立体选择性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  DOI：

  10.1002/ejoc.200400829

文献信息

• Enantio-and stereo-selective route to the taxol side chain via asymmetric epoxidation of trans-cinnamyl alcohol and subsequent expoxide ring opening
  作者：Carlo Bonini、Giuliana Righi

  DOI：10.1039/c39940002767

  日期：——

  The first route to the side chain of Taxol and Taxotere, employing asymmetric epoxidation (AE) of trans-cinnamyl alochol and a new highly regio- and stereo-selective opening to the epoxide ring with MgBr2, is described.

  报道了第一条通向紫杉醇和多西他赛侧链的路线，该路线采用反式肉桂醇的不对称环氧化（AE）以及与MgBr2的新型高度区域选择性和立体选择性环氧环开环反应。
• Reaction of Alkenes with Hydrogen Peroxide and Sodium Iodide: A Nonenzymatic Biogenic-Like Approach to Iodohydrins
  作者：José Barluenga、María Marco-Arias、Francisco González-Bobes、Alfredo Ballesteros、José M. González

  DOI：10.1002/chem.200305582

  日期：2004.4.2

  An efficient protocol to synthesize iodohydrins from alkenes is presented. Reactions were conducted in aqueous media using safe and readily available sodium iodide (the most abundant form of the element), and a highly convenient oxidant such as hydrogen peroxide. Addition of a protic acid triggers a faster and efficient process, a role formally related to that played by haloperoxidase enzymes in naturally

  提出了从烯烃合成碘代醇的有效方案。反应使用安全易得的碘化钠（元素的最丰富形式）和高度方便的氧化剂（如过氧化氢）在水性介质中进行。质子酸的添加会触发更快，更有效的过程，这一作用与卤代过氧化物酶在自然发生的转化中所起的作用正式相关。还讨论了将这些条件成功应用于多克级制剂和天然产物衍生物的过程。
• Synthesis of Bromo- and Iodohydrins from Deactivated Alkenes by Use ofN-Bromo- andN-Iodosaccharin
  作者：Damijana Urankar、Irena Rutar、Barbara Modec、Darko Dolenc

  DOI：10.1002/ejoc.200400829

  日期：2005.6

  N-Bromo and N-iodosaccharin react with electron-deficient alkenes such as α,β-unsaturated ketones, acids, esters and nitriles in aqueous organic solvents, yielding the corresponding halohydrins in good yields. The reactions take place at room temperature, mostly within short reaction times and with high antistereoselectivity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  N-溴和 N-碘糖精在水性有机溶剂中与缺电子烯烃如 α,β-不饱和酮、酸、酯和腈反应，以良好的收率生成相应的卤代醇。反应在室温下进行，大部分反应时间短且具有高抗立体选择性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Free radicals and Lewis acid. Chelation-controlled radical allylations of substituted α-halo- or α-phenylseleno-β-alkoxy esters. The endocyclic effect.
  作者：B Guérin、C Chabot、N Mackintosh、W W Ogilvie、Y Guindon

  DOI：10.1139/v00-074

  日期：2000.6.1

  The radical allylation of a series of α-halo or α-phenylseleno-β-alkoxy esters in the presence of MgBr₂·OEt₂ is reported and compared with analogous reactions under non-chelating conditions. The addition of MgBr₂·OEt₂ gives excellent selectivity favoring anti products; in some cases ratios >100:1 are obtained. Varying the substrate substituents reveals that these reactions are quite tolerant of alkyl functionalities at the β-position. Changes to the alkoxy function indicate that a chelate is involved in the reaction. The reactions are successful with secondary iodides, bromides, and phenylselenides, as well as tertiary iodides, which all give very high ratios under chelation control. Performing less well under the same conditions are substrates with a radical exocyclic to a tetrahydrofuran ring. EDTA titration is used to determine the amount of Mg²⁺ dissolved in the allylation reaction mixture, and ¹³C NMR is employed to better define the nature of the complex formed (chelate or monodentate) prior to the reaction. Competition experiments suggest that the chelate and monodentate pathways are in competition for the radical allylation with allyltributyltin.Key words: allylation, radicals, Lewis acid, stereoselectivity, 1,2-induction.

  报道了在MgBr2·OEt2存在下的一系列α-卤代或α-苯基硒烷基酯的基团联化反应，并与非螯合条件下的类似反应进行了比较。添加MgBr2·OEt2具有良好的选择性，有利于产生反式产物；在某些情况下，可获得大于100:1的比率。改变底物取代基表明，这些反应对β-位置的烷基官能团相当耐受。烷氧基功能的变化表明，反应中涉及到螯合物。这些反应对于次碘化物、溴化物和苯基硒化物以及三级碘化物都很成功，所有这些底物在螯合控制下都给出非常高的比率。在相同条件下表现不佳的是具有四氢呋喃环外端基团的底物。使用EDTA滴定法确定了在基团联化反应混合物中溶解的Mg2+的数量，使用13C NMR更好地定义了反应前形成的络合物的性质（螯合物或单齿）。竞争实验表明，螯合和单齿途径在基团联化反应中与丁烯基三丁基锡竞争。关键词：基团联化，自由基，路易斯酸，立体选择性，1,2-归位作用。
• A simple route to syn α-Amino-β-Hydroxy esters by C-2 regioselective opening of a, β-Epoxy esters with metal halides
  作者：Giuliana Righi、Giovanna Rumboldt、Carlo Bonini

  DOI：10.1016/0040-4020(95)00873-7

  日期：1995.11

  α,β-Epoxy esters are opened by NaX (X = I, Br) in a regio and stereoselective fashion to β-hydroxy-α-halo esters, which represent suitable precursors of syn α-amino-β-hydroxy esters and β-hydroxy esters.

  NaX（X = I，Br）以区域和立体选择性的方式将α，β-环氧酯打开为β-羟基-α-卤代酯，β-羟基-α-卤代酯代表合成α-氨基-β-羟基酯和β-羟基酯。