methyl (E)-2-benzylidene-5-phenylpent-4-ynoate

• 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: methyl (E)-2-benzylidene-5-phenylpent-4-ynoate
• 英文别名: (E)-methyl-2-benzylidene-5-phenylpent-4-ynoate；methyl (2E)-2-benzylidene-5-phenylpent-4-ynoate
• 化学式: C₁₉H₁₆O₂
• 分子量: 276.335
• InChiKey: MAHWBIOVTIXSFF-OBGWFSINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  methyl (E)-2-benzylidene-5-phenylpent-4-ynoate 在 硫酸 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以41%的产率得到methyl 9-phenyl-7H-benzocycloheptenecarboxylate
  参考文献：
  名称：

  Synthesis of methyl 9-phenyl-7H-benzocycloheptene-6-carboxylates from Baylis–Hillman adducts: use of intramolecular Friedel–Crafts alkenylation reaction

  摘要：

  We developed a facile synthetic method for 9-phenyl-7H-benzocycloheptene derivatives from the Baylis-Hillman adducts. Our method involved intramolecular Friedel-Crafts alkenylation reaction of triple bond-tethered methyl cinnamates. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.06.057
• 作为产物：
  描述：

  2-(phenyl((3-phenylpropioloyl)oxy)methyl)acrylate 在 四(三苯基膦)钯 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以83%的产率得到methyl (E)-2-benzylidene-5-phenylpent-4-ynoate
  参考文献：
  名称：

  高度区域选择性和立体选择性的Pd催化串联烯丙基重排/分子内脱羧反应，衍生自Baylis-Hillman加合物的芳基丙酸酯

  摘要：

  已经开发出高度区域选择性和立体选择性的Pd催化串联烯丙基重排/分子内脱羧的衍生自Baylis-Hillman醇的丙酸芳酯，导致形成一类重要的1,5-二芳基戊-1-烯-4-炔。丙烯酸甲酯衍生的Baylis–Hillman醇的芳基丙酸酯仅提供（E）-1,5-二芳基-1-en-4-ynes，而丙烯腈衍生的Baylis–Hillman醇的芳基丙酸酯仅提供（Z）-1 ，5-二芳基戊-1-烯-4-炔。

  DOI：

  10.1016/j.tetlet.2015.02.125

文献信息

• Pd-catalyzed decarboxylative allylic coupling of acetates of Baylis–Hillman alcohols with propiolic acids: a highly regio- and stereoselective synthesis of 1,5-diarylpent-1-en-4-yne derivatives
  作者：Satyanarayana Tummanapalli、Parthasarathy Muthuraman、Dhanunjaya Naidu Vangapandu、Gnanakalai Shanmugavel、Sanjeeva Kambampati、Kee Wei Lee

  DOI：10.1039/c5ra06168g

  日期：——

  happened via an exclusively SN2′ pathway. Acetates of the Baylis–Hillman alcohols derived from alkyl acrylates, ethyl vinyl ketone and phenyl vinyl sulfone provided exclusively (E)-1,5-diarylpent-1-en-4-ynes while the acetates of the Baylis–Hillman alcohols derived from acrylonitrile provided exclusively (Z)-1,5-diarylpent-1-en-4-ynes.

  Pd催化Baylis-Hillman醇的乙酸酯与炔基羧酸的乙酸脱羧烯丙基偶联导致以高度区域和立体选择性的方式形成重要的1,5-二芳基戊-1-烯-4-炔。脱羧偶联仅通过S N 2'途径发生。衍生自丙烯酸烷基酯，乙基乙烯基酮和苯基乙烯基砜的Baylis-Hillman醇的乙酸盐仅提供（E）-1,5-二芳基戊-1-烯-4-炔，而Baylis-Hillman醇的乙酸盐则衍生自丙烯腈专门提供（Z）-1,5-diarylpent-1-en-4-ynes。
• Dehydrative and Decarboxylative Coupling of Alkynoic Acids with Allylic Alcohols
  作者：Peizhong Xie、Ju Qiu、Jingwei Hou、Zuolian Sun

  DOI：10.1055/a-1750-3080

  日期：2022.6

  A direct dehydroxylative and decarboxylative coupling between a large number of allylic alcohols and alkynoic acids was realized affording 1,4-enyne motifs in high efficiency. In this reaction, calcium-promoted C–OH bond cleavage was crucial, which facilitated the sequential ­decarboxylation, and thus enabled the palladium-catalyzed allyl­–alkynyl coupling, which occurred in an environmentally benign

  实现了大量烯丙醇和炔酸之间的直接脱羟基和脱羧偶联，从而高效地提供了 1,4-烯炔基序。在该反应中，钙促进的 C-OH 键断裂是至关重要的，这促进了顺序脱羧，从而使钯催化的烯丙基-炔基偶联成为可能，这种偶联以一种环境友好的方式发生，可耐受多种官能团。该协议已成功用于制备克级抗癌活性鲁珀罗衍生物。
• Indium-mediated alkynylation of Baylis–Hillman acetates: a novel route to 1,4-enynes
  作者：Jhillu S. Yadav、Basi V. Subba Reddy、Nagendra Nath Yadav、Ashutosh Pratap Singh、Madavi Choudhary、Ajit C. Kunwar

  DOI：10.1016/j.tetlet.2008.08.019

  日期：2008.10

  Baylis-Hillman acetates undergo smooth alkynylation with aryl-susbstituted iodoalkynes in the presence of indium metal in refluxing dichloromethane to furnish 1,4-enynes in high yields with (E)-stereoselectivity. In the absence of Lewis acid, the reaction follows both S(N)2 and S(N)2' pathways affording 1:1 mixtures of 1,4-enynes. Upon addition of 10 mol % of InBr(3), the reaction proceeds preferably in the S(N)2' manner. In the case of adducts derived from acrylonitrile, the corresponding products are obtained in fairly good yields and with (Z)-stereoselectivity. (C) 2008 Elsevier Ltd. All rights reserved.