methyl (S)-(ethenyloxy)(phenyl)acetate | 167702-71-8

• 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: methyl (S)-(ethenyloxy)(phenyl)acetate
• 英文别名: methyl (2S)-2-ethenoxy-2-phenylacetate
• CAS: 167702-71-8
• 化学式: C₁₁H₁₂O₃
• 分子量: 192.214
• InChiKey: KGNQMSVXINQFBZ-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (S)-(ethenyloxy)(phenyl)acetate 在 lithium aluminium tetrahydride 、 tris(6,6,7,7,8,8-heptafluoro-2,2-dimethyl-3,5-octadionato)europium(III) 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 mineral oil 为溶剂， 反应 44.0h， 生成 (2R,4R)-2-[(S)-2-(benzyloxy)-1-phenylethoxy]-4-[(2,3,4,6-tetra-O-benzyl-β-D-mannopyranosyl)methyl]-6-(thiazol-2-yl)-3,4-dihydro-2H-pyran
  参考文献：
  名称：

  Stereoselective preparation of four 3-C-mannosylated d- and l-glucals from a single starting compound

  摘要：

  The corresponding oxadiene, prepared from the starting perbenzylated alpha-D-mannopyranosylethanal was subjected to stereoselective cycloaddition reactions with R and S methyl (ethenyloxy)(phenyl)acetates. From the two obtained diastereoisomeric cycloadducts, 3-C-alpha-D-mannosylated 1,2-D-glucal and 3-C-alpha-D-mannosylated 1,2-L-glucal were prepared. A simple epimerisation of the starting alpha-D-mannopyranosylethanal afforded perbenzylated beta-D-mannopyranosylethanal, which was converted to 3-C-beta-D-mannosylated 1,2-D-glucal or to 3-C-beta-D-mannosylated 1,2-L-glucal by the same procedure. The structure of the obtained 3-C-alpha-D-mannosylated 1,2-D-glucal has been confirmed independently by its transformation to the known peracetylated methyl alpha-C-(1 -> 3)-mannobioside. The prepared glucals are suitable precursors for the synthesis of stable glycoconjugates with non-hydrolyzable mannose-containing epitopes. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.04.044
• 作为产物：
  描述：

  L-扁桃酸甲酯 在 三氟甲磺酸三甲基硅酯 、 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 137.0h， 生成 methyl (S)-(ethenyloxy)(phenyl)acetate
  参考文献：
  名称：

  高效无水制备手性仲醇和α-羟基酯的乙烯基和异丙烯基醚

  摘要：

  易于从α-手性醇1a-h和乙基乙烯基醚或异丙烯基甲基醚衍生而来的混合缩醛2a-h和5a-d，在用三乙胺和三甲基甲硅烷基三氟甲磺酸酯处理后，选择性地除去了伯醇，因此得到了良好的高分别得到手性烯醇醚3a-h和6a-d的产率。

  DOI：

  10.1016/0040-4039(95)00087-s

文献信息

• Hetero Diels-Alder Reactions of 2-Chloro-1nitroso-1-phenylethene: Preparation of Novel 4-Chloro-Substituted 1,2-Oxazins and Subsequent Reactions
  作者：Reinhold Zimmer、Jörg Angermann、Ute Hain、Florian Hiller、Hans-Ulrich Reissig

  DOI：10.1055/s-1997-1373

  日期：1997.12

  The cycloaddition of 2-chloro-1-nitroso-1-phenylethene (3), generated in situ from 2,2-dichloro-1-phenylethan-1-one oxime (2) to electron-rich olefins, e.g. silyl enol ethers or alkyl enol ethers, furnished the 4-chloro-substituted 5,6-dihydro-4H-1,2-oxazines and 6H-1,2 oxazines in moderate to good yields and with good diastereoselectivities. Bromo enol ether 18 led to the unexpected α,α-dichloro oxime derivative 21 as well as the halogenated 6H-1,2-oxazines 19 and 20. Starting from 4-chloro-1,2-oxazines 5 and 17, 4-azido-, 4-amino-, 4-hydroxy-, and 4-oxo-substituted 1,2-oxazines were prepared. Hydrogenolysis of 5,6-dihydro-4H-1,2-oxazine 5 afforded amine 31.

  在电子丰富的烯烃，例如硅醚醇或烷基醚醇存在下，2-氯-1-亚硝基-1-苯乙烯（3），由2,2-二氯-1-苯乙酮肟（2）原位生成，经过环加成反应，以中等到良好的产率和良好的非对映选择性得到4-氯取代的5,6-二氢-4H-1,2-嗪和6H-1,2-嗪。溴醚醇18意外地产生了α,α-二氯肟衍生物21以及卤代的6H-1,2-嗪19和20。以4-氯-1,2-嗪5和17为起始物，合成了4-叠氮基、4-氨基、4-羟基和4-氧代取代的1,2-嗪。氢解5,6-二氢-4H-1,2-嗪5得到了胺31。
• An approach to stereoselective preparation of 3-C-glycosylated d- and l-glucals
  作者：Kamil Parkan、Lukáš Werner、Zuzana Lövyová、Eva Prchalová、Ladislav Kniežo

  DOI：10.1016/j.carres.2009.11.025

  日期：2010.2

  corresponding alpha- or beta-glycopyranosylethanals is described. The key step of the approach is the stereoselective cycloaddition of chiral vinyl ethers derived from both enantiomers of mandelic acid. The preparation of 1,5-anhydro-4,6-di-O-benzyl-2,3-dideoxy-3-C-[(2,3,4,6-tetra-O-benzyl-beta-D-glucopyranosyl)methyl]-L-arabino-hex-1-enitol, 1,5-anhydro-4,6-di-O-benzyl-2,3-dideoxy-3-C-[(2,3,4,6-tetra-O-benzyl

  描述了一种从相应的α-或β-甘露聚糖核糖体开始立体选择性合成α-或β-3-C-糖基化的L-或D-1,2-葡萄糖的方法。该方法的关键步骤是衍生自扁桃酸两个对映异构体的手性乙烯基醚的立体选择性环加成反应。1,5-脱水-4,6-二-O-苄基-2,3-二脱氧-3-C-[（2,3,4,6-四-O-苄基-β-D-吡喃葡萄糖基）甲基] -L-阿拉伯-己-1-烯醇，1,5-脱水-4,6-二-O-苄基-2,3-二脱氧-3-C-[（2,3,4,6-四-O-苄基-β-D-吡喃葡萄糖基）甲基] -D-阿拉伯糖基-己-1-烯醇和1,5-脱水-4,6-二-O-苄基-2,3-二脱氧-3- C-[（2,3,4-三-O-苄基-α-L-呋喃核糖基）甲基] -D-阿拉伯糖基己基-1-烯醇用作该方法的一个实例。
• Stereoselective Preparation of Precursors of α-C-(1→3)-Disaccharides
  作者：Petr Štěpánek、Ondřej Vích、Lukáš Werner、Ladislav Kniežo、Hana Dvořáková、Pavel Vojtíšek

  DOI：10.1135/cccc20051411

  日期：——

  The stereoselectivity of cycloaddition of sugar-containing substituted 1-(thiazol-2-yl)but-2-en-1-ones 1 and vinyl ethers was studied using the achiral vinyl ether/chiral catalyst as well as the chiral vinyl ether/achiral catalyst combinations. It has been shown that Eu(fod)₃-catalyzed cycloaddition of oxadienes 1a-1e with the chiral vinyl ethers 9 and 10 affords stereoselectively almost pure cycloadducts 11a-11e and 12a-12e, respectively. The obtained cycloadducts are suitable precursors for the synthesis of α-C-(1→3)-disaccharides, containing 2-deoxy-arabino-hexopyranose moiety of D- or L-configuration.

  糖基取代的1-(噻唑-2-基)丁-2-烯-1-酮1和乙烯醚的环加成立体选择性研究，使用了非手性乙烯醚/手性催化剂和手性乙烯醚/非手性催化剂组合。研究表明，欧洲铕（fod）3催化的氧代二烯1a-1e与手性乙烯醚9和10的环加成，分别选择性地得到了几乎纯的环加成产物11a-11e和12a-12e。所得的环加成产物是合成α-C-(1→3)-二糖的合适前体，包含D或L构型的2-脱氧-阿拉伯-己糖基。
• Eu(fod) 3 -catalyzed solid-phase [4+2] heterocycloadditions: an efficient asymmetric process in catalyst-recycling conditions
  作者：Gilles Dujardin、Stéphane Leconte、Ludovic Coutable、Eric Brown

  DOI：10.1016/s0040-4039(01)01921-9

  日期：2001.12

  Under Eu(fod)3-catalyzed conditions, the endo-selective hetero Diels–Alder reaction of (S)-(+)-O-vinyl mandelate with Wang-supported benzylidenepyruvate occurred with a 93/7 facial selectivity that compares well with those observed in solution. In addition, the solid-phase sequence allowed an unprecedented reuse of the catalyst in the presence of excess dienophile in solution.

  在Eu（fod）3催化条件下，（S）-（+）- O-乙烯基扁桃酸酯与Wang负载的亚苄基丙酮酸酯的内选择性杂Diels-Alder反应发生，其面部选择性为93/7在溶液中观察到。另外，固相序列允许在溶液中存在过量亲双烯体的情况下催化剂的空前重复使用。
• Stereoselective Preparation of 2,3-Dideoxy-3-C-[(α-D-galactopyranosyl)methyl]-D-arabino-hexopyranose and 2,3-Dideoxy-3-C-[(α-D-galactopyranosyl)methyl]-L-arabino-hexopyranose
  作者：Kamil Parkan、Ondřej Vích、Hana Dvořáková、Ladislav Kniežo

  DOI：10.1135/cccc20080690

  日期：——

  The diastereomeric substituted 2H-dihydropyran derivatives 2b and 3b were obtained by the stereoselective cycloaddition of (E)-4-(tetra-O-benzyl-α-D-galactopyranosyl)-1-(thiazol-2-yl)but-2-en-1-one (1) with either of the enantiomeric chiral vinyl ethers (R)-4 or (S)-4. Reduction of the ester group, transformation of the thiazole ring into an aldehyde group and reaction with an excess of borane afforded the final C-(1→3)-disaccharide structures. The obtained C-(1→3)-disaccharides, containing an L- or D-deoxy-arabino-hexopyranose moiety at the reducing end, were characterized as peracetylated methyl glycosides 9a, 9b and 12a, 12b.

  通过手性选择性环加成反应，使用手性乙烯醚（R）-4或（S）-4与（E）-4-（四-O-苄基-α-D-半乳糖苷基）-1-（噻唑-2-基）丁-2-烯-1-酮（1）反应，得到了对映异构的取代2H-二氢吡喃衍生物2b和3b。酯基还原，噻唑环转化为醛基，并与过量硼烷反应，得到最终的C-(1→3)-二糖结构。所得到的C-(1→3)-二糖结构，包含一个L-或D-去氧-阿拉伯-六元糖苷基在还原端，被表征为过乙酰化的甲基糖苷9a、9b和12a、12b。