ethyl 3-(5-methylthiophen-2-yl)propiolate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 3-(5-methylthiophen-2-yl)propiolate
• 英文别名: Ethyl 3-(5-methylthiophen-2-yl)prop-2-ynoate；ethyl 3-(5-methylthiophen-2-yl)prop-2-ynoate
• 化学式: C₁₀H₁₀O₂S
• 分子量: 194.254
• InChiKey: NSYZDRBAETZODW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  54.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 3-(5-methylthiophen-2-yl)propiolate 、 在 三丁基膦 、 十二/十四烷基二甲基氧化胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 13.0h， 以53%的产率得到ethyl 2-{[9-borabicyclo[3.3.1]nonan-9-yl](5-methylthiophen-2-yl)methylene}-3-[9-oxa-10-borabicyclo[3.3.2]decan-10-yl]octanoate
  参考文献：
  名称：

  膦催化的基于9-BBN的1,1-二硼烷基烷烃的炔烃抗碳硼化反应：多取代的γ-芳基烯丙二烯的合成与应用

  摘要：

  三烷基膦有机催化能够使炔烃与基于9-BBN的1,1-二硼烷基烷烃进行区域选择性抗碳负硼化反应，生成具有β-烷氧基羰基和γ-硼烷基取代基的仲烯丙基硼烷。N-（三甲基甲硅烷基）醛亚胺的高度非对映选择性烯丙基化反应可生产出高密度官能化的烯丙基硼烷，以生产含有叔烯丙基硼烷和丙烯酸酯部分的高烯丙基胺。

  DOI：

  10.1002/anie.201712351

文献信息

• Synthesis of Trisubstituted Alkenylstannanes through Copper-Catalyzed Three-Component Coupling of Alkylboranes, Alkynoates, and Tributyltin Methoxide
  作者：Takamichi Wakamatsu、Kazunori Nagao、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1002/anie.201305973

  日期：2013.10.25

  A versatile route to trisubstituted alkenylstannanes is presented. The alkyl and Sn moieties were introduced at the β and α carbon atoms of alkynoates, respectively, in a formal syn addition mode with complete regioselectivity (see scheme). A variety of functional groups were tolerated in the alkylboranes and alkynoates.

  提出了一种通用的途径来制备三取代的链烯基锡烷。烷基和Sn部分分别以正式的顺式 加成模式和完全的区域选择性引入炔烃的β和α碳原子上（参见方案）。烷基硼烷和炔酸酯中可耐受多种官能团。
• Phosphine-Catalyzed Vicinal Acylcyanation of Alkynoates
  作者：Hiroaki Murayama、Kazunori Nagao、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1021/acs.orglett.6b00677

  日期：2016.4.1

  Phosphine organocatalysis enabled vicinal acylcyanation of alkynoates with acyl cyanides to form acrylonitrile derivatives with a tetrasubstituted alkene moiety. The acyl and cyano groups were introduced at the α and β carbon atoms, respectively, of the C–C triple bond in the alkynoates with complete regioselectivity and high anti stereoselectivity. A variety of functional groups in the acyl cyanides

  膦有机催化能够使炔酸酯与酰基氰化物一起进行邻位酰基氰化，以形成具有四取代烯烃部分的丙烯腈衍生物。酰基和氰基分别在炔烃的C–C三键的α和β碳原子处引入，具有完全的区域选择性和高的立体抗选择性。酰基氰化物和炔酸中的多种官能团是可以耐受的。
• Phosphine-Catalyzed <i>Anti</i>-Hydroboration of Internal Alkynes
  作者：Kazunori Nagao、Ayaka Yamazaki、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1021/acs.orglett.8b00390

  日期：2018.4.6

  Trialkylphosphine organocatalysts have enabled regioselective anti-hydroboration of internal, alkynes with pinacolborane reagents to provide (E)-disubstituted alkenylboronate compounds. The alkenyl-boronate can be used for derivatizations, such as protodeborylation, Suzuld-Miyaura coupling, conjugate reduction, and Diels-Alder reactions.
• <i>Anti</i>-Selective Vicinal Silaboration and Diboration of Alkynoates through Phosphine Organocatalysis
  作者：Kazunori Nagao、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1021/acs.orglett.5b00305

  日期：2015.3.6

  Trialkylphosphine organocatalysts have enabled anti-selective vicinal silaboration and diboration of the C-C triple bond in alkynoates to produce beta-boryl-alpha-silyl acrylates and alpha,beta-diboryl acrylates, respectively. The anti stereoselectivity was complete and robust. A variety of functional groups were tolerated in the alkynoates. The two vicinally installed heteroatom substituents of the beta-boryl-alpha-silyl acrylates and alpha,beta-diboryl acrylates could be differentiated and transformed in a stepwise manner, allowing the synthesis of a diverse array of unsymmetrical tetrasubstituted alkenes.
• Phosphine-Catalyzed <i>Anti</i>-Carboboration of Alkynoates with Alkyl-, Alkenyl-, and Arylboranes
  作者：Kazunori Nagao、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1021/ja506310v

  日期：2014.7.30

  We found that trialkylphosphine organo-catalysts promoted unprecedented anti-carboboration of alkynoates with alkyl-, alkenyl-, or arylboranes to form beta-boryl acrylates. The regioselectivity of the carboboration across the polar C-C triple bond exhibited inverse electronic demand, with the less electronegative B atom being delivered to the positively charged beta carbon atom. The regioselectivity and the anti stereoselectivity were both complete and robust. In addition, the substrate scope was broad with excellent functional group compatibility.