5-(benzylthio)pent-1-en-3-yl acetate

• 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: 5-(benzylthio)pent-1-en-3-yl acetate
• 英文别名: 3-acetoxy-5-(benzylthio)-1-pentene；5-Benzylsulfanylpent-1-en-3-yl acetate
• 化学式: C₁₄H₁₈O₂S
• 分子量: 250.362
• InChiKey: BIAHVLXCEVHYER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-硝基丙烷 、 5-(benzylthio)pent-1-en-3-yl acetate 在 、 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 以83%的产率得到(S)-benzyl(3-(2-nitropropan-2-yl)pent-4-en-1-yl)sulfane
  参考文献：
  名称：

  对映选择性铱催化硝基烷烃的烯丙基化：生成 β-立体异构 α-季伯胺

  摘要：

  描述了铱催化烯丙基烷基化中简单硝基亲核试剂的首次系统研究。使用tol-BINAP修饰的π-烯丙基铱C , O-苯甲酸酯催化剂，α,α-二取代硝基化合物取代外消旋支链烷基取代的烯丙基乙酸酯，从而提供β-立体异构α-季伯胺的入口。 DFT 计算揭示了早期过渡态，使反应对空间效应和非对映手性铱 π-烯丙基络合物的明显反式效应不太敏感，从而促进了拥挤的三级-四级 C-C 键的形成。

  DOI：

  10.1021/jacs.1c05212
• 作为产物：
  描述：

  3-苄基硫代丙腈 在 4-二甲氨基吡啶 、 正丁基锂 、 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 、 苯 为溶剂， 反应 2.5h， 生成 5-(benzylthio)pent-1-en-3-yl acetate
  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

• Ethanol: Unlocking an Abundant Renewable C ₂ ‐Feedstock for Catalytic Enantioselective C−C Coupling
  作者：Cole C. Meyer、Nicholas P. Stafford、Melinda J. Cheng、Michael J. Krische

  DOI：10.1002/anie.202102694

  日期：2021.5.3

  production at >85 million tons/year, ethanol is the world's largest‐volume renewable small molecule carbon source, yet its use as a C2‐feedstock in enantioselective C−C coupling is unknown. Here, the first catalytic enantioselective C−C couplings of ethanol are demonstrated in reactions with structurally complex, nitrogen‐rich allylic acetates incorporating the top 10 N‐heterocycles found in FDA‐approved

  乙醇的年产量超过 8500 万吨/年，是世界上产量最大的可再生小分子碳源，但其在对映选择性 C−C 偶联中作为 C 2原料的用途尚不清楚。在这里，乙醇的第一个催化对映选择性 C−C 偶联在与结构复杂、富含氮的烯丙乙酸酯的反应中得到证实，其中含有 FDA 批准的药物中发现的前 10 个氮杂环。
• Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides
  作者：Xiao-Feng Ren、Edward Turos、Charles H. Lake、Melvyn Rowen Churchill

  DOI：10.1021/jo00125a038

  日期：1995.10

  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.
• Enantioselective Iridium-Catalyzed Allylation of Nitroalkanes: Entry to β-Stereogenic α-Quaternary Primary Amines
  作者：Woo-Ok Jung、Binh Khanh Mai、Brian J. Spinello、Zachary J. Dubey、Seung Wook Kim、Craig E. Stivala、Jason R. Zbieg、Peng Liu、Michael J. Krische

  DOI：10.1021/jacs.1c05212

  日期：2021.6.30

  The first systematic study of simple nitronate nucleophiles in iridium-catalyzed allylic alkylation is described. Using a tol-BINAP-modified π-allyliridium C,O-benzoate catalyst, α,α-disubstituted nitronates substitute racemic branched alkyl-substituted allylic acetates, thus providing entry to β-stereogenic α-quaternary primary amines. DFT calculations reveal early transition states that render the

  描述了铱催化烯丙基烷基化中简单硝基亲核试剂的首次系统研究。使用tol-BINAP修饰的π-烯丙基铱C , O-苯甲酸酯催化剂，α,α-二取代硝基化合物取代外消旋支链烷基取代的烯丙基乙酸酯，从而提供β-立体异构α-季伯胺的入口。 DFT 计算揭示了早期过渡态，使反应对空间效应和非对映手性铱 π-烯丙基络合物的明显反式效应不太敏感，从而促进了拥挤的三级-四级 C-C 键的形成。