4-methoxy-α-deuterostyrene | 193361-04-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-methoxy-α-deuterostyrene
• 英文别名: 1-(p-methoxyphenyl)ethylene-1-d1；1-(1-deuteriovinyl)-4-methoxybenzene；α-deuterio-1-methoxy-4-vinylbenzene；α-deuterio-4-ethenylanisole；1-(1-Deuterioethenyl)-4-methoxybenzene；1-(1-deuterioethenyl)-4-methoxybenzene
• CAS: 193361-04-5
• 化学式: C₉H₁₀O
• 分子量: 135.17
• InChiKey: UAJRSHJHFRVGMG-WFVSFCRTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-methoxy-α-deuterostyrene 在 四氧化锇 水 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 为溶剂， 以61%的产率得到1-(4-methoxyphenyl)-[1-²H]-ethane-1,2-diol
  参考文献：
  名称：

  Kinetic Isotope Effects in Cycloreversion of Rhenium (V) Diolates

  摘要：

  Cycloreversion of 4-methoxystyrene from the corresponding Tp'Re(O)(diolato) complex (Tp' = hydrido-tris-(3,5-dimethylpyrazolyl)borate) was measured competitively for various isotopomers at 103 degreesC. Primary (C-12/C-13) and seconclar / (H-1/H-2) kinetic isotope effects were determined. The primary KIEs were k(12C)/k(13C) = 1.041 +/- 0.005 at the alpha position and 1.013 +/- 0.006 at the beta position. Secondary KIEs were k(H)/k(D) = 1.076 +/- 0.005 at the alpha position and 1.017 +/- 0.005 at the beta position. Computational modeling (B3LYP/LACVP*+) located a transition state for concerted cycloreversion of styrene from TpRe(O)(OCH2CHPh) exhibiting dramatically different C-O bond lengths. A Hammett study on cycloreversions of substituted styrenes from a series of Tp'Re(O)(diolato) showed dichotomous behavior for electron donors and electron-withdrawing groups as substituents: rho = -0.65 for electron donors, but rho = +1.13 for electron-withdrawing groups. The data are considered in light of various mechanistic proposals. While the extrusion of 4-methoxystyrene is concluded to be a highly asynchronous concerted reaction, the Hammett study reflects a likelihood that multiple reaction mechanisms are involved.

  DOI：

  10.1021/ja017736w
• 作为产物：
  描述：

  4-甲氧基苯基-1,1-D2-甲醇 在 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 4-methoxy-α-deuterostyrene
  参考文献：
  名称：

  Kinetic Isotope Effects in Cycloreversion of Rhenium (V) Diolates

  摘要：

  Cycloreversion of 4-methoxystyrene from the corresponding Tp'Re(O)(diolato) complex (Tp' = hydrido-tris-(3,5-dimethylpyrazolyl)borate) was measured competitively for various isotopomers at 103 degreesC. Primary (C-12/C-13) and seconclar / (H-1/H-2) kinetic isotope effects were determined. The primary KIEs were k(12C)/k(13C) = 1.041 +/- 0.005 at the alpha position and 1.013 +/- 0.006 at the beta position. Secondary KIEs were k(H)/k(D) = 1.076 +/- 0.005 at the alpha position and 1.017 +/- 0.005 at the beta position. Computational modeling (B3LYP/LACVP*+) located a transition state for concerted cycloreversion of styrene from TpRe(O)(OCH2CHPh) exhibiting dramatically different C-O bond lengths. A Hammett study on cycloreversions of substituted styrenes from a series of Tp'Re(O)(diolato) showed dichotomous behavior for electron donors and electron-withdrawing groups as substituents: rho = -0.65 for electron donors, but rho = +1.13 for electron-withdrawing groups. The data are considered in light of various mechanistic proposals. While the extrusion of 4-methoxystyrene is concluded to be a highly asynchronous concerted reaction, the Hammett study reflects a likelihood that multiple reaction mechanisms are involved.

  DOI：

  10.1021/ja017736w

文献信息

• Palladium-Catalyzed Synthesis of Deuterated Alkenes through Deuterodechlorination of Alkenyl Chlorides
  作者：Masami Kuriyama、Gemba Yano、Hirotoshi Kiba、Tetsuro Morimoto、Kosuke Yamamoto、Yosuke Demizu、Osamu Onomura

  DOI：10.1021/acs.oprd.9b00193

  日期：2019.8.16

  of alkenyl chlorides has been developed, and a variety of deuterated alkenes were synthesized with precise control of the deuterium incorporation. This catalytic process tolerates heterocyclic moieties and frameworks derived from bioactive agents. In addition to the double incorporation of deuterium, the gram-scale synthesis of a deuterated iminostilbene unit including a core substructure of carbamazepine

  已经开发了钯催化的链烯基氯化物的氘代脱氯作用，并通过精确控制氘的掺入合成了多种氘代的烯烃。该催化过程容许衍生自生物活性剂的杂环部分和骨架。除了氘的两次掺入外，还以高产率和优异的氘化程度完成了包括卡马西平核心亚结构的氘代亚氨基二苯乙烯单元的克级合成。
• Mechanism of the [2 + 2] Photocycloaddition of Fullerene C₆₀ with Styrenes
  作者：Georgios Vassilikogiannakis、Maria Hatzimarinaki、Michael Orfanopoulos

  DOI：10.1021/jo0006223

  日期：2000.12.1

  op-1-ene-3,3,3-d(3) (trans-5-d(3)) to C(60) is attributed to a steric kinetic isotope effect (k(H)/k(D) = 0.78). The loss of stereochemistry in the cyclobutane ring excludes a concerted addition and is consistent with a stepwise mechanism. Intermolecular secondary kinetic isotope effects of the [2 + 2] photocycloaddition of 3-d(0) vs 3-d(1), and 3-d(6) as well as 5-d(0) vs 5-d(1), and 5-d(6) to C(60)

  立体化学研究[2 + 2]光加成的顺式/反式-4-丙烯基茴香醚（顺式-1和反式1）和顺式-1-（对甲氧基苯基）乙烯-2-d（1）（顺式-3- d（1））到C（60）在前者中表现出立体特异性，而反式2环加合物表现出立体选择性。在光化学添加（E）-1-（对甲氧基苯基）-2-甲基-丙氧基的情况下，观察到的立体选择性有利于cis-6-d（3）[2 + 2]非对映异构体12％。 C（60）的1-ene-3,3,3-d（3）（trans-5-d（3））归因于空间动力学同位素效应（k（H）/ k（D）= 0.78） 。环丁烷环中立体化学的损失排除了一致的加成，并且与逐步机理一致。3-d（0）与3-d（1）和3-d（6）以及5-d（0）与5-d（1）的[2 + 2]光环加成的分子间二级动力学同位素效应），还测量了5-d（6）至C（60）。由于两个乙烯基氢在3的β-碳原子上被氘取代而引起的分子间竞争表现出实质性的反向α-次级同位素效应k（H）/
• α-Selective Ni-Catalyzed Hydroalumination of Aryl- and Alkyl-Substituted Terminal Alkynes: Practical Syntheses of Internal Vinyl Aluminums, Halides, or Boronates
  作者：Fang Gao、Amir H. Hoveyda

  DOI：10.1021/ja104896b

  日期：2010.8.18

  A method for Ni-catalyzed hydroalumination of terminal alkynes, leading to the formation of alpha-vinylaluminum isomers efficiently (>98% conv in 2-12 h) and with high selectivity (95% to >98% alpha), is described. Catalytic alpha-selective hydroalumination reactions proceed in the presence of a reagent (diisobutylaluminum hydride; dibal-H) and 3.0 mol % metal complex (Ni(dppp)Cl(2)) that are commercially

  描述了一种用于末端炔烃的 Ni 催化加氢铝化的方法，可有效地形成 α-乙烯基铝异构体（在 2-12 小时内转化率 >98%）并具有高选择性（95% 至 >98% α）。催化 α 选择性氢化铝化反应在试剂（二异丁基氢化铝；dibal-H）和 3.0 mol% 金属配合物（Ni(dppp)Cl(2)) 的存在下进行，这些金属配合物是市售且价格低廉的。在相同条件下，但使用 Ni(PPh(3))(2)Cl(2) 时，加氢铝化具有高度的 beta 选择性，并且与使用 dibal-H 的未催化转化不同，生成很少或不生成炔铝副产品。所有加氢金属化反应都是可靠的、操作简单且实用的，并且提供了各种不容易获得的乙烯基铝。衍生的α-乙烯基卤化物和硼酸酯可以通过用合适的亲电子试剂[例如，分别为Br(2)和甲氧基(频哪醇)硼]直接处理来合成。Ni 催化的氢氧化铝可以使用低至 0.1 mol% 的催化剂以克级规模进行，具有同样高的效率和选择性。
• Catalytic, Directed C–C Bond Functionalization of Styrenes
  作者：Shunsuke Onodera、Ryo Togashi、Soya Ishikawa、Takuya Kochi、Fumitoshi Kakiuchi

  DOI：10.1021/jacs.0c02232

  日期：2020.4.22

  A method for catalytic conversion of C(aryl)-C(alkenyl) bonds in styrene derivatives to new C-C bonds is developed. In the presence of a rhodium catalyst, the alkenyl groups of styrenes bearing a pyrazolyl directing group were efficiently converted to other carbon substituents upon reacting with various alkenes including styrenes, aliphatic alkenes, and allyl alcohols. It is also indicated that the

  开发了一种将苯乙烯衍生物中的 C(芳基)-C(烯基)键催化转化为新 CC 键的方法。在铑催化剂的存在下，带有吡唑基导向基团的苯乙烯的烯基在与包括苯乙烯、脂肪族烯烃和烯丙醇在内的各种烯烃反应时有效地转化为其他碳取代基。还表明CC键断裂是通过氢金属化/β-碳消除途径进行的。
• Modified Shapiro Reactions with Bismesitylmagnesium As an Efficient Base Reagent
  作者：William J. Kerr、Angus J. Morrison、Marek Pazicky、Tina Weber

  DOI：10.1021/ol300652k

  日期：2012.5.4

  Bismesitylmagnesium has been shown to successfully mediate the Shapiro reaction. A range of tosylhydrazones has been subjected to the developed system, which furnishes exceptionally high incorporation of the introduced electrophiles and good yields of the functionalized styrenes. At conveniently accessible temperatures and with a comparably small excess of base reagent, this protocol offers an efficient alternative to the lithium-mediated process. Importantly, 1.05 equiv of Welnreb amides are sufficient to obtain aryl enones in good yields.