(Z)-methyl 2-(bromomethyl)-3-(3-methoxyphenyl)acrylate | 171366-47-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (Z)-methyl 2-(bromomethyl)-3-(3-methoxyphenyl)acrylate
• 英文别名: methyl 3-(3-methoxyphenyl)-2-(bromomethyl)propenoate；methyl (Z)-2-(bromomethyl)-3-(3-methoxyphenyl)prop-2-enoate
• CAS: 171366-47-5
• 化学式: C₁₂H₁₃BrO₃
• 分子量: 285.137
• InChiKey: DJZQNKJCPDGKPR-UXBLZVDNSA-N

物化性质

• 沸点：
  349.7±37.0 °C(Predicted)
• 密度：
  1.398±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  (Z)-methyl 2-(bromomethyl)-3-(3-methoxyphenyl)acrylate 在 三乙烯二胺 、 manganese(IV) oxide 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 0.5h， 生成 2-(3-methoxybenzyl)acrylaldehyde
  参考文献：
  名称：

  On the stereochemistry of the Baker's Yeast-mediated reduction of regioisomeric unsaturated aldehydes: Examples of enantioselectivity switch promoted by substrate-engineering

  摘要：

  The Baker's Yeast (BY) reduction of (Z)-2-chloromethyl-3-arylacrylaldehydes was found to afford (R)-2-methyl-3-aryl-propanols showing high enantiomeric excess values. Deuterium incorporation experiments were performed, in order to investigate the mechanism of the bioreduction: the formation of the corresponding substituted 2-benzylacrylaldehydes. as intermediates to be effectively reduced by Baker's Yeast, was suggested. These intermediates were synthesized and submitted to BY reduction to afford the corresponding saturated (R)-alcohols, thus confirming the conclusions drawn from labelling experiments. The enantioselectivity of their bioreduction was found to be opposite with respect to that observed for the corresponding regioisomeric 2-methylcinnamaldehydes. The preparation of the two enantiomers of 2-methyl-3-aryl-propanols by fermentation of two regioisomers represents an interesting example of substrate-controlled enantioselective reaction. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2012.02.003
• 作为产物：
  描述：

  3-甲氧基苯甲醛 在 三乙烯二胺 、 硫酸 、 氢溴酸 作用下， 以 二氯甲烷 、 水 为溶剂， 生成 (Z)-methyl 2-(bromomethyl)-3-(3-methoxyphenyl)acrylate
  参考文献：
  名称：

  On the stereochemistry of the Baker's Yeast-mediated reduction of regioisomeric unsaturated aldehydes: Examples of enantioselectivity switch promoted by substrate-engineering

  摘要：

  The Baker's Yeast (BY) reduction of (Z)-2-chloromethyl-3-arylacrylaldehydes was found to afford (R)-2-methyl-3-aryl-propanols showing high enantiomeric excess values. Deuterium incorporation experiments were performed, in order to investigate the mechanism of the bioreduction: the formation of the corresponding substituted 2-benzylacrylaldehydes. as intermediates to be effectively reduced by Baker's Yeast, was suggested. These intermediates were synthesized and submitted to BY reduction to afford the corresponding saturated (R)-alcohols, thus confirming the conclusions drawn from labelling experiments. The enantioselectivity of their bioreduction was found to be opposite with respect to that observed for the corresponding regioisomeric 2-methylcinnamaldehydes. The preparation of the two enantiomers of 2-methyl-3-aryl-propanols by fermentation of two regioisomers represents an interesting example of substrate-controlled enantioselective reaction. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2012.02.003

文献信息

• 2,3-Dichloro-5,6-dicyano-<i>para</i>-benzoquinone (DDQ)/Methanesulfonic Acid (MsOH)-Mediated Intramolecular Arene-Alkene Oxidative Coupling
  作者：Ko Hoon Kim、Cheol Hee Lim、Jin Woo Lim、Jae Nyoung Kim

  DOI：10.1002/adsc.201301169

  日期：2014.3.10

  An efficient intramolecular arene‐alkene oxidative coupling of 1,4‐diaryl‐1,3‐butadienes has been developed involving the use of a 2,3‐dichloro‐5,6‐dicyano‐para‐benzoquinone (DDQ)/acid catalyst. The reaction involves the generation of a radical cation by abstraction of an electron from the substrate with DDQ, an intramolecular Friedel–Crafts‐type reaction, and the loss of hydrogen radical.

  已经开发出一种有效的1,4-二芳基-1,3-丁二烯分子内芳烃-烯烃氧化偶联方法，其中涉及使用2,3-二氯-5,6-二氰基对对苯二酚（DDQ）/酸催化剂。该反应涉及通过用DDQ从底物中提取电子来产生自由基阳离子，分子内Friedel-Crafts型反应以及氢自由基的损失。
• Palladium-Catalyzed Construction of Spirooxindoles by Arylative Cyclization of 3-(γ,δ-Disubstituted)allylidene-2-Oxindoles
  作者：Ko Hoon Kim、Hye Ran Moon、Junseong Lee、Jae Nyoung Kim

  DOI：10.1002/adsc.201400965

  日期：2015.3.9

  afforded spirodihydronaphthalene‐2‐oxindole frameworks via an oxidative Heck arylation (Fujiwara–Moritani reaction), an allylic palladium migration, and an aryl CH bond functionalization/arylation cascade of reactions. This is a first example of the palladium‐catalyzed oxidative arylation and an aryl CH bond functionalization/arylation cascade reaction which involves an electrophilic arylative quenching

  钯催化的3-（γ，δ-二取代）亚芳基-2-氧吲哚的一锅芳基环化反应通过氧化Heck芳基化反应（Fujiwara-Moritani反应）提供了螺二氢萘-2-氧吲哚骨架，烯丙基钯迁移和芳基CH键官能化/芳基化反应级联。这是钯催化的氧化芳基化的第一示例和芳基C 涉及的亲电子arylative淬火H键官能/芳基化级联反应的π烯丙基中间体和一个区域-受控的芳基C  H键活化由辅助钯-芳烃相互作用弱。
• Convergent stereocontrolled construction of 5-7-6 tricyclic aza analogues of phorbol and aconite alkaloids
  作者：Charles M. Marson、Jennifer H. Pink、Christopher Smith

  DOI：10.1016/0040-4039(95)01688-e

  日期：1995.10

  An acyliminium cyclization is used to construct the central seven-membered ring of 5-7-6 tricyclic aza-analogues of diterpenoids.
• An Asymmetric Synthesis of Aza Analogues of the Tricyclic Skeleton of Daphnane and the ABC Ring System of Phorbol
  作者：Charles M. Marson、Jennifer H. Pink、David Hall、Michael B. Hursthouse、Abdul Malik、Christopher Smith

  DOI：10.1021/jo0205816

  日期：2003.2.1

  An asymmetric synthesis of aza analogues of the ABC ring system of phorbol and related compounds containing the 5-7-6-fused framework of daphnane involved construction of the central seven-membered ring by a regioselective reduction of a chiral imide and cyclization with trifluoromethanesulfonic acid. Subsequent demethylation and oxidative dearomatization of ring C afforded an enantiopure dienone 20 with the same relative and absolute configuration at the 9- and 10-positions of the phorbol skeleton.
• On the stereochemistry of the Baker's Yeast-mediated reduction of regioisomeric unsaturated aldehydes: Examples of enantioselectivity switch promoted by substrate-engineering
  作者：Elisabetta Brenna、Giovanni Fronza、Claudio Fuganti、Francesco G. Gatti、Alessia Manfredi、Fabio Parmeggiani、Paolo Ronchi

  DOI：10.1016/j.molcatb.2012.02.003

  日期：2012.12

  The Baker's Yeast (BY) reduction of (Z)-2-chloromethyl-3-arylacrylaldehydes was found to afford (R)-2-methyl-3-aryl-propanols showing high enantiomeric excess values. Deuterium incorporation experiments were performed, in order to investigate the mechanism of the bioreduction: the formation of the corresponding substituted 2-benzylacrylaldehydes. as intermediates to be effectively reduced by Baker's Yeast, was suggested. These intermediates were synthesized and submitted to BY reduction to afford the corresponding saturated (R)-alcohols, thus confirming the conclusions drawn from labelling experiments. The enantioselectivity of their bioreduction was found to be opposite with respect to that observed for the corresponding regioisomeric 2-methylcinnamaldehydes. The preparation of the two enantiomers of 2-methyl-3-aryl-propanols by fermentation of two regioisomers represents an interesting example of substrate-controlled enantioselective reaction. (C) 2012 Elsevier B.V. All rights reserved.