(Z)-2-bromo-1-phenylvinyl acetate | 99511-02-1

• 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: (Z)-2-bromo-1-phenylvinyl acetate
• 英文别名: [(Z)-2-bromo-1-phenylethenyl] acetate
• CAS: 99511-02-1
• 化学式: C₁₀H₉BrO₂
• 分子量: 241.084
• InChiKey: RNRRHOHDFSTXBJ-YFHOEESVSA-N

物化性质

• 沸点：
  280.0±29.0 °C(Predicted)
• 密度：
  1.444±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-2-bromo-1-phenylvinyl acetate 在 甲酸铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 以89%的产率得到2,5-二苯基吡嗪
  参考文献：
  名称：

  Highly efficient synthesis of 2,5-disubstituted pyrazines from (Z)-β-haloenol acetates

  摘要：

  描述了一种高效合成多种2,5-二取代吡嗪的方法，该方法源自(Z)-β-卤烯醇醋酸酯。在便利的条件下进行反应，所产物具有优异的区域选择性，产率中等至优秀，并且适用范围广泛，包括多种芳香族和脂肪族卤烯醇醋酸酯。

  DOI：

  10.1039/c3ob41164h
• 作为产物：
  描述：

  2,2-二溴-1-苯乙酮 在 sodium tetrahydroborate 、 正丁基锂 、 二异丙胺 作用下， 以 甲醇 为溶剂， 反应 12.58h， 生成 (Z)-2-bromo-1-phenylvinyl acetate
  参考文献：
  名称：

  Ester homologation revisited: a reliable, higher yielding and better understood procedure

  摘要：

  Enolate anions 3 and 6, prepared via enolization of a-bromo and dibromo ketones 4 and 5 were converted m high yield to ynolate anions 10 by respective addition of lithium tetramethylpiperidide (to effect deprotonation, 3 --> 7) or butyllithium (to effect metal-halogen exchange, 6 --> 7). Mixtures of such enolates were abo obtainable from esters 1 m a large-scale (25 mmol) via in situ formation and addition of lithiodibromomethane (from methylene bromide and lithium tetramethylpiperidide), followed by treatment of the resulting adducts with lithium hexamethyldisilazide to ensure complete enolization. Addition of sec-butyllithium and n-butyllithium to effect ynolate anion formation, followed by quenching of the reaction mixtures into acidic ethanol, reproducibly afforded homologated esters 8 in 67-90% yield. Demonstrated for ethyl esters 1 having the carbethoxy moiety attached to primary, secondary, tertiary, aryl, and alkenyl groups, this general procedure provides a convenient, large-scale alternative to the classical Arndt-Eistert sequence.

  DOI：

  10.1021/jo00052a038

文献信息

• Synthesis of 2,5-Disubstituted 3-Iodofurans via Palladium-Catalyzed Coupling and Iodocyclization of Terminal Alkynes
  作者：Zhengwang Chen、Gao Huang、Huanfeng Jiang、Huawen Huang、Xiaoyan Pan

  DOI：10.1021/jo1023987

  日期：2011.2.18

  2,5-Disubstituted 3-iodofurans are readily prepared under very mild reaction conditions by the palladium/copper-catalyzed cross-coupling of (Z)-β-bromoenol acetates and terminal alkynes, followed by iodocyclization. The useful intermediates conjugated enyne acetates are obtained in high yields in the transformation. Aryl- and alkyl-substituted alkynes undergo iodocyclization in good yields. The resulting

  通过钯/铜催化的（Z）-β-溴烯醇乙酸酯和末端炔烃的钯/铜催化交叉偶联，然后碘环化，可以在非常温和的反应条件下轻松制备2,5-二取代的3-碘呋喃。在转化中以高收率获得了有用的中间体共轭烯炔乙酸酯。芳基和烷基取代的炔烃以高收率进行碘环化。所得的含碘的呋喃可以容易地加工成2,3,5-三取代的呋喃。
• The Palladium–Catalyzed Cross-Coupling Reaction of Enol Acetates of α-Bromo Ketones with 1-Alkenyl-, Aryl-, or Alkylboron Compounds; A Facile Synthesis of Ketones and Their Enol Acetates
  作者：Shigeru Abe、Norio Miyaura、Akira Suzuki

  DOI：10.1246/bcsj.65.2863

  日期：1992.10

  The synthesis of stereodefined enol acetates of ketones is readily accomplished by palladium–catalyzed cross-coupling reaction between alkyl-, aryl-, or 1-alkylboron reagents with enol acetates of α-bromo ketones. Hydroboration of alkene with 9-BBN, followed by coupling with (Z)-2-ethoxy-1-bromoethene gives the enol ether of aldehyde. These enol acetates and ethers are readily deprotected to give corresponding

  酮的立体定义的烯醇乙酸酯的合成很容易通过钯催化的烷基-、芳基-或 1-烷基硼试剂与 α-溴酮的烯醇乙酸酯之间的交叉偶联反应来完成。烯烃与 9-BBN 的硼氢化反应，然后与 (Z)-2-乙氧基-1-溴乙烯偶联得到醛的烯醇醚。这些烯醇乙酸酯和醚很容易脱保护，以高产率得到相应的酮和醛。
• Silver-Catalyzed Difunctionalization of Terminal Alkynes: Highly Regio- and Stereoselective Synthesis of (<i>Z</i>)-β-Haloenol Acetates
  作者：Zhengwang Chen、Jinghao Li、Huanfeng Jiang、Shifa Zhu、Yibiao Li、Chaorong Qi

  DOI：10.1021/ol101251n

  日期：2010.7.16

  A new silver-catalyzed highly regio- and stereoselective difunctionalization reaction of simple terminal alkynes was reported in which the (Z)-β-haloenol acetate derivatives were formed efficiently. The resulting products were versatile intermediates in organic synthesis.

  报道了一种新的银催化的简单末端炔烃的高度区域和立体选择性双官能化反应，其中有效地形成了（Z）-β-卤代烯醇乙酸酯衍生物。所得产物是有机合成中的通用中间体。
• Catalyst- and Metal-Free Rapid Functionalizations of Alkynes Using TsNBr2
  作者：Lal Yadav、Ruchi Chawla、Atul Singh

  DOI：10.1055/s-0033-1339194

  日期：——

  A very rapid (3–12 min) and efficient method has been developed for a one-pot synthesis of α,α-dibromoalkanones and β-bromoenol alkanoates directly from alkynes using N , N -dibromo- p -toluenesulfonamide (TsNBr 2 ). The protocol is embellished with features like ambient temperature, high regioselectivity, operational simplicity, and metal- and catalyst-free conditions.

  已经开发了一种非常快速（3-12 分钟）且有效的方法，用于使用 N , N - 二溴对甲苯磺酰胺 (TsNBr 2 ) 直接从炔烃一锅合成 α,α-二溴链烷酮和 β-溴烯醇链烷酸酯。该协议具有环境温度、高区域选择性、操作简单以及无金属和无催化剂条件等特点。
• A Highly Efficient Synthesis of 2,5-Disubstituted Furans from Enyne Acetates Catalyzed by Lewis Acid and Palladium
  作者：Zheng-Wang Chen、Liang-Xian Liu、Miao-Ting Luo、Yue-Lu Wen、Min Ye、Zhong-Gao Zhou

  DOI：10.1055/s-0034-1379213

  日期：——

  A highly efficient synthesis of a wide range of 2,5-disubstituted furans from enyne acetates is described. The reactions are conducted by using Lewis acid and palladium catalyst and provide symmetrical and unsymmetrical products in good to excellent yields, with broad substrate scope, including a variety of aromatic and aliphatic substituents in the 2- and 5-position of the furan ring.

  描述了一种从醋酸烯炔高效合成各种 2,5-二取代呋喃的方法。该反应是通过使用路易斯酸和钯催化剂进行的，并以良好到极好的收率提供对称和不对称产物，底物范围广泛，包括呋喃环的 2 位和 5 位的各种芳香族和脂肪族取代基。