N-(tert-butoxycarbonyl)-4-(1-hexynyl)piperidin-4-yl methyl carbonate | 1082069-15-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: N-(tert-butoxycarbonyl)-4-(1-hexynyl)piperidin-4-yl methyl carbonate
• 英文别名: BocC5H8N(OCO2Me)CCBu；Tert-butyl 4-hex-1-ynyl-4-methoxycarbonyloxypiperidine-1-carboxylate
• CAS: 1082069-15-5
• 化学式: C₁₈H₂₉NO₅
• 分子量: 339.432
• InChiKey: RNQMMPBHRAIOGI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-(tert-butoxycarbonyl)-4-(1-hexynyl)piperidin-4-yl methyl carbonate 在 copper diacetate 、 4,5-双二苯基膦-9,9-二甲基氧杂蒽 作用下， 以 四氢呋喃 为溶剂， 以44%的产率得到tert-butyl 4-(hex-1-enylidene)piperidine-1-carboxylate
  参考文献：
  名称：

  The synthesis of allenes by Cu(i)-catalyzed regio- and stereoselective reduction of propargylic carbonates with hydrosilanes

  摘要：

  铜(I)催化的反SN2'型内丙炔碳酸酯与氢硅烷的还原反应可以高选择性地产生多种二取代和三取代的烯烃；该反应与功能基团兼容，并且在合成光学活性烯烃方面表现出高效性。

  DOI：

  10.1039/b910192f
• 作为产物：
  描述：

  tert-butyl 4-(hex-1-yn-1-yl)-4-hydroxypiperidine-1-carboxylate 、 氯甲酸甲酯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 N-(tert-butoxycarbonyl)-4-(1-hexynyl)piperidin-4-yl methyl carbonate
  参考文献：
  名称：

  Copper(I)-Catalyzed Substitution of Propargylic Carbonates with Diboron: Selective Synthesis of Multisubstituted Allenylboronates

  摘要：

  A versatile synthetic method for the preparation of the allenylboronates, Cu(I)-catalyzed reaction of propargylic carbonates with a diboron, is described. A Cu(O-t-Bu)-Xantphos catalyst system was effective for the preparation of various allenylboron compounds, allenylboronates with different substitution patterns, those with functional groups, and an axially chiral one. The Lewis acid promoted stereoselective addition to aldehydes leading to homopropargylic alcohols showed the usefulness of the new allenylboronates.

  DOI：

  10.1021/ja806602h

文献信息

• The synthesis of allenes by Cu(i)-catalyzed regio- and stereoselective reduction of propargylic carbonates with hydrosilanes
  作者：Chongmin Zhong、Yusuke Sasaki、Hajime Ito、Masaya Sawamura

  DOI：10.1039/b910192f

  日期：——

  Cu(I)-catalyzed anti-SN2′-type reduction of internal propargylic carbonates with hydrosilanes affords various di- and trisubstituted allenes with high regioselectivities; the reactions are compatible with functional groups and work efficiently for the synthesis of optically-active allenes.

  铜(I)催化的反SN2'型内丙炔碳酸酯与氢硅烷的还原反应可以高选择性地产生多种二取代和三取代的烯烃；该反应与功能基团兼容，并且在合成光学活性烯烃方面表现出高效性。
• General and Functional Group-Tolerable Approach to Allenylsilanes by Rhodium-Catalyzed Coupling between Propargylic Carbonates and a Silylboronate
  作者：Hirohisa Ohmiya、Hideto Ito、Masaya Sawamura

  DOI：10.1021/ol902339a

  日期：2009.12.17

  The Rh-catalyzed coupling reaction between propargylic carbonates and a silylboronate afforded allenylsilanes with different substitution patterns in high yields. The reaction tolerates a variety of functional groups in propargylic carbonates. The reaction of an optically active propargylic carbonate proceeded with excellent chirality transfer with 1,3-anti stereochemistry to give an axially chiral

  炔丙基碳酸酯和甲硅烷基硼酸酯之间的Rh催化的偶联反应以高收率提供了具有不同取代方式的烯丙基硅烷。该反应可耐受炔丙基碳酸酯中的各种官能团。旋光的碳酸炔丙酯的反应以优异的手性转移与1，3-抗立体化学进行，得到轴向手性的烯丙基硅烷。
• Deoxygenative Silylation of C(sp³)–O Bonds with Hydrosilane by Cooperative Catalysis of Gold Nanoparticles and Solid Acids
  作者：Hiroki Miura、Yuki Yasui、Yosuke Masaki、Masafumi Doi、Tetsuya Shishido

  DOI：10.1021/acscatal.3c00973

  日期：2023.5.19

  Efficient deoxygenative silylation of C(sp3)–O bonds with hydrosilanes by supported Au catalysts is described. Gold nanoparticles supported on TiO2 enabled various hydrosilanes to be used as sources of silyl groups in C–Si cross-coupling reactions. A variety of alkyl acetates and propargyl carbonates participated in the Au-catalyzed reactions to furnish the corresponding alkyl and allenylsilanes in

  描述了负载型 Au 催化剂对 C(sp 3 )–O 键与氢硅烷的有效脱氧硅烷化。负载在 TiO 2上的金纳米粒子使各种氢硅烷能够在 C-Si 交叉偶联反应中用作甲硅烷基的来源。各种乙酸烷基酯和碳酸炔丙酯参与了金催化的反应，以高产率提供相应的烷基和烯丙基硅烷。此外，Au/TiO 2对环醚的开环甲硅烷基化也有效。详细的机理研究证实标题反应涉及甲硅烷基和烷基自由基中间体的形成，而 Au 纳米颗粒作为单电子转移催化剂与金属氧化物表面的路易斯酸位点的合作是氢硅烷异常反应性的原因特定的 C(sp 3 )–Si 键形成。
• Copper(I)-Catalyzed Substitution of Propargylic Carbonates with Diboron: Selective Synthesis of Multisubstituted Allenylboronates
  作者：Hajime Ito、Yusuke Sasaki、Masaya Sawamura

  DOI：10.1021/ja806602h

  日期：2008.11.26

  A versatile synthetic method for the preparation of the allenylboronates, Cu(I)-catalyzed reaction of propargylic carbonates with a diboron, is described. A Cu(O-t-Bu)-Xantphos catalyst system was effective for the preparation of various allenylboron compounds, allenylboronates with different substitution patterns, those with functional groups, and an axially chiral one. The Lewis acid promoted stereoselective addition to aldehydes leading to homopropargylic alcohols showed the usefulness of the new allenylboronates.
• Hydride-free reduction of propargyl electrophiles: a nickel-catalyzed photoredox strategy for allene synthesis
  作者：Tingjun Hu、Vincent Fagué、Didier Bouyssi、Nuno Monteiro、Abderrahmane Amgoune

  DOI：10.1039/d4gc00984c

  日期：——

  catalytic reduction of propargyl carbonates to allenes mediated by a nickel molecular catalyst. The catalytic system uses light as the driving force and amine as the sole hydrogen source. Contrary to other catalytic approaches, the process proceeds without the intermediacy of metal hydride species. The commonly observed pathway in transition metal catalyzed reductive processes is replaced by a pathway

  在此，我们报道了由镍分子催化剂介导的碳酸炔丙酯催化还原为丙二烯。该催化系统使用光作为驱动力，胺作为唯一的氢源。与其他催化方法相反，该过程的进行无需金属氢化物物质的中介。过渡金属催化还原过程中常见的途径被涉及一系列电子转移和质子转移的途径所取代。使用这种催化方法，可以在温和条件下获得多种丙二烯。实验研究支持三烷基胺作为还原剂和质子源的双重作用，并揭示了该反应的关键机理特征。提出了Ni( II ) 联烯基中间体的关键原脱镍步骤来解释还原过程。最后，我们还证明选择性 S N 2 ' 还原过程也可以通过电化学方法有效驱动。