(E)-2-(2-(phenylthio)vinyl)pyridine | 1398413-99-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (E)-2-(2-(phenylthio)vinyl)pyridine
• 英文别名: 2-(2-(phenylthio)vinyl)pyridine
• CAS: 1398413-99-4
• 化学式: C₁₃H₁₁NS
• 分子量: 213.303
• InChiKey: GLJPZQIGNMYIGA-PKNBQFBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  12.89
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  2-乙炔基吡啶 、 苯磺酰肼 在 1,8-diazabicyclo[5.4.0]undec-7-en-8-ium acetate 、 溶剂黄146 作用下， 反应 0.08h， 以50%的产率得到
  参考文献：
  名称：

  Regioselective Hydrothiolation of Alkynes by Sulfonyl Hydrazides Using Organic Ionic Base–Brønsted Acid

  摘要：

  A practical and novel approach has been developed for the synthesis of vinyl sulfides by the reaction of sulfonyl hydrazides with aryl/heteroarylacetylenes using a DBU-based ionic liquid. The system offers a new sulfur source for hydrothiolation and is endowed with green credentials.

  DOI：

  10.1021/ol401925u

文献信息

• Design of Highly Selective Alkyne Hydrothiolation Rh^I-NHC Catalysts: Carbonyl-Triggered Nonoxidative Mechanism
  作者：Laura Palacios、Yoann Meheut、María Galiana-Cameo、María José Artigas、Andrea Di Giuseppe、Fernando J. Lahoz、Victor Polo、Ricardo Castarlenas、Jesús J. Pérez-Torrente、Luis A. Oro

  DOI：10.1021/acs.organomet.7b00251

  日期：2017.6.12

  deprotonation of the thiol to generate the RhI active species, whereas the π-acceptor character of the carbonyl ligand hinders the oxidative addition process. In addition, the stereochemistry of the key thiolate-π-alkyne intermediate, which is determined by the electronic preference of the carbonyl ligand to coordinate cis to IPr, facilitates the rate-limiting alkyne thiometalation step.

  已经制备了带有N，O-吡啶-2-甲醇-（NO）二齿配体的新的Rh I -IPr（IPr ＝ 1，3-双（2，6-二异丙基苯基）咪唑啉-2-卡宾）配合物。羰基配合物Rh（NO）（IPr）（CO）有效催化一系列炔烃的氢硫醇化反应，对α-乙烯基硫化物具有高选择性。反应性研究和DFT计算揭示了一条新的非氧化催化途径，该途径通过Rh I催化中间体，这是由吡啶-2-甲醇基和羰基配体之间的相互作用驱动的。碱性烷氧基配体促进巯基的去质子化以生成Rh I活性物种，而羰基配体的π受体特性阻碍了氧化加成过程。另外，关键的硫醇盐-π-炔中间体的立体化学是由羰基配体的电子偏好决定，以将顺式配位至IPr，这有利于限速炔硫金属化步骤。
• A Recyclable Biphasic System for Stereoselective and Easily Handled Hydrochalcogenations
  作者：Caterina Tidei、Luca Sancineto、Luana Bagnoli、Benedetta Battistelli、Francesca Marini、Claudio Santi

  DOI：10.1002/ejoc.201402668

  日期：2014.9

  Vinyl selenides and vinyl sulfides were prepared by hydrochalcogenation of alkynes with selenols and thiols generated in situ by the reduction of the corresponding diselenides and disulfides with elemental zinc in a biphasic acidic medium. The yields, stereoselectivity as well as the possibility of reusing the aqueous medium up to ten times are discussed.

  通过在双相酸性介质中用元素锌还原相应的二硒化物和二硫化物而原位生成的硒醇和硫醇，通过炔烃与硒醇和硫醇的氢化硫属化反应制备乙烯基硒化物和乙烯基硫化物。讨论了产率、立体选择性以及将水性介质重复使用多达十次的可能性。
• Hydroxo–Rhodium–N-Heterocyclic Carbene Complexes as Efficient Catalyst Precursors for Alkyne Hydrothiolation
  作者：Laura Palacios、Maria Jose Artigas、Victor Polo、Fernando J. Lahoz、Ricardo Castarlenas、Jesús J. Pérez-Torrente、Luis A. Oro

  DOI：10.1021/cs400739y

  日期：2013.12.6

  The new Rh-hydroxo dinuclear complexes stabilized by an N-heterocyclic carbene (NHC) ligand of type [Rh(mu-OH)(NHC)(eta(2)-olefin)](2) (coe, IPr (3), IMes (4); ethylene, IPr (5)) are efficient catalyst precursors for alkyne hydrothiolation under mild conditions, presenting high selectivity toward alpha-vinyl sulfides for a varied set of substrates, which is enhanced by pyridine addition. The structure of complex 3 has been determined by X-ray diffraction analysis. Several intermediates relevant for the catalytic process have been identified, including Rh-I-thiolato species Rh(SCH2Ph)(IPr)(eta(2)-coe)(py) (6) and Rh(SCH2Ph)(IPr)(eta(2)-HC CCH2Ph)(py) (7), and the Rh-III-hydride-dithiolato derivative RhH(SCH2Ph)(2)(IPr)(py) (8) as the catalytically active species. Computational DFT studies reveal an operational mechanism consisting of sequential thiol deprotonation by the hydroxo ligand, subsequent S-H oxidative addition, alkyne insertion, and reductive elimination. The insertion step is rate-limiting with a 1,2 thiometalation of the alkyne as the more favorable pathway in accordance with the observed Markovnikov-type selectivity.