benzyl pent-1-yn-5-yl sulfide | 148470-61-5

• 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: benzyl pent-1-yn-5-yl sulfide
• 英文别名: 5-(benzylthio)-1-pentyne；4-pentynyl benzyl sulfide；benzyl(pent-4-yn-1-yl)sulfane；Pent-4-ynylsulfanylmethylbenzene
• CAS: 148470-61-5
• 化学式: C₁₂H₁₄S
• 分子量: 190.309
• InChiKey: BFCOFDMEVMHGPH-UHFFFAOYSA-N

物化性质

• 沸点：
  283.5±23.0 °C(Predicted)
• 密度：
  1.023±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  benzyl pent-1-yn-5-yl sulfide 在 碘 、 间氯过氧苯甲酸 作用下， 生成 (E)-2-(iodomethylene)tetrahydrothiophene 1,1-dioxide
  参考文献：
  名称：

  Regiochemical studies on halocyclization reactions of unsaturated sulfides

  摘要：

  DOI：

  10.1016/0040-4039(93)85010-t
• 作为产物：
  描述：

  5-碘-1-戊炔 、 硫代乙酸苄酯 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以92%的产率得到benzyl pent-1-yn-5-yl sulfide
  参考文献：
  名称：

  Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides

  摘要：

  The regiochemistry and stereochemistry for the halocyclization reactions of unsaturated benzyl sulfides have been examined as a function of tether length, type of unsaturation (carbon-carbon double bond versus carbon-carbon triple bond), substituents, and halogenating agent. Alkenyl sulfides were found to react with iodine or bromine at room temperature to give five-membered ring cycloadducts exclusively over those having four-membered rings, while for larger systems, six-membered ring products are formed preferentially over their five-membered ring isomers and exclusively over the seven-membered ring adducts. The endo- versus exo-regioselectivity of these alkenyl sulfide ring closures most likely reflects the difference in thermodynamic stabilities of the beta-halo sulfide cycloadducts, which are able to equilibrate via a common episulfonium intermediate. The efficiency of the cyclization process markedly drops off for these alkenyl sulfides as the tether length increases beyond four intervening carbon centers. Thus, while the halogenations of 3-butenyl sulfides and 4-pentenyl sulfides give high yields of cycloadducts, those of 5-hexenyl sulfides afford only small amounts of cyclized products and large quantities of acyclic dibromides. Conversely the reactions of acetylenic sulfides with iodine give uniformly high yields and regiochemical control regardless of the tether length. Thus, 3-butynyl and 4-pentynyl sulfides cyclize cleanly to the five-membered ring while 5-hexynyl sulfides give exclusively the six-membered ring, The products arising from these alkynyl sulfide ring closures are believed to be formed under kinetic control. The methodology has been applied to the synthesis of unusual bicyclic beta-lactams related to the penicillin family of antibiotics.

  DOI：

  10.1021/jo00125a038

文献信息

• Fromα,β-Unsaturated Fischer Carbene Complexes to Highly Substituted 3-Ethoxycyclopentadienes, Masked Cyclopentenones
  作者：Yao-Ting Wu、Bernard Flynn、Heiko Schirmer、Frank Funke、Stefan Müller、Thomas Labahn、Markus Nötzel、Armin de Meijere

  DOI：10.1002/ejoc.200300534

  日期：2004.2

  cyclopentenones 21 could be either eliminated or transformed into other functional groups via the quaternary ammonium salts 24. The elimination product, cyclopentadienone 27 can undergo dimerization either by a formal [4+2] or [2+2] cycloaddition. Cyclopentenone 21naaa with a bromovinyl-terminated side chain undergoes an intramolecular Heck reaction to form 5-methyl-4,6-dimethylenebicyclo[3.3.0]oct-1-en-3-one

  β-氨基取代的 α,β-不饱和 Fischer 卡宾配合物 3 很容易通过四步一锅法从末端炔烃、六羰基铬和仲胺中获得（24 个实例的产率为 68-99%，7 个实例的产率26-63%）。配合物 3 与不同炔烃（包括二炔和烯炔）在供体溶剂（如吡啶或乙腈）中进行正式的 [3+2] 环加成，得到高度取代的 5-（二烷基氨基）-3-乙氧基环戊二烯 7，通常产率中等至极好（25 个例子）产率为 60-95% 和 7 个实施例的产率为 18-53%）。卡宾配合物上的取代基和引入的炔烃对成环反应的区域和立体选择性的空间和电子效应已经详细说明。一个有趣的 1,5- 或更可能的 1，对于在 C-5 处具有三甲基甲硅烷基和 iPr 取代基的 5-(二甲氨基)-3-乙氧基环戊二烯，观察到二甲氨基的 2-迁移。尝试从具有手性氨基或取代基的配合物 3 不对称合成环戊二烯 7 仅取得了中等程度的成功。在仲氨基的手性中心，类型
• Palladium‐Catalyzed Regiodivergent Synthesis of 1,3‐Dienyl and Allyl Esters from Propargyl Esters
  作者：Mengfu Dai、Zhimin Sun、Liang‐An Chen

  DOI：10.1002/anie.202203835

  日期：2022.6.7

  An unprecedented catalyst-controlled regiodivergent strategy has been developed that allows efficient access to structurally diverse 1,3-dienyl and allyl esters from common propargyl esters with high regio- and stereochemical outcomes. The ligand backbone is crucial for the regioselectivity pattern, enabling the palladium catalyst to involve electrophilic metal catalysis or sequential oxidative addition–reductive

  已经开发了一种前所未有的催化剂控制的区域发散策略，该策略允许从具有高区域和立体化学结果的常见炔丙基酯中有效地获得结构多样的 1,3-二烯基和烯丙基酯。配体主链对于区域选择性模式至关重要，使钯催化剂能够参与亲电子金属催化或顺序氧化加成-还原消除途径。
• Tin Radical Addition to Alkynyl Sulfides: Reactivity of the Intermediate Thioalkyl-Substituted .beta.-(Tributylstannyl)vinyl Radicals
  作者：Laura Capella、Pier Carlo Montevecchi、Daniele Nanni

  DOI：10.1021/jo00091a025

  日期：1994.6

  Phenyl and benzyl alkynyl sulfides 1a-g and 3a, phenylalkynylamines 19a,b, ethers 22a,b, and selenide 31 reacted with tributyltin radicals to give intermediate beta-stannylvinyl radicals, whose fate depended on the nature of the side chain. 4-Phenylthio-substituted but-1-en-2-yl radicals underwent stereospecific 5-exo cyclization on the adjacent phenyl ring. The resulting spirocyclohexadienyl radicals gave thiophenes and thiopyrans by carbon-sulfur bond scission or ring expansion on the exocyclic double bond, respectively. Similar behavior was exhibited by the corresponding selenium-containnig radical, which afforded a selenophene almost exclusively. (Benzylthio) alkyl-substituted radicals gave products deriving from intramolecular S(H)2 substitution at the sulfur atom, whereas propargyl sulfides yielded a stannylallene via a beta-scission reaction. No 6(or more)-membered ring closure was observed with pentynyl and hexynyl phenyl sulfides 1b,c, which gave only the (E)-addition products of tin hydride; oxygen- and nitrogen-containing vinyl radicals also gave the (E)-adducts exclusively. An interaction between the unpaired electron orbital and the empty low-energy orbitals of the heteroatom might explain why sulfur and selenium can undergo 5-exo cyclization.
• Regiochemical studies on halocyclization reactions of unsaturated sulfides
  作者：Ren Xiao-Feng、Edward Turos

  DOI：10.1016/0040-4039(93)85010-t

  日期：1993.3
• Capella Laura, Montevecchi Pier Carlo, Nanni Daniele, J. Org. Chem, 59 (1994) N 12, S 3368- 3374
  作者：Capella Laura, Montevecchi Pier Carlo, Nanni Daniele

  DOI：——

  日期：——