1-t-butoxycarbonyl-2-tributylstannylpiperidine | 123387-55-3

• 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: 1-t-butoxycarbonyl-2-tributylstannylpiperidine
• 英文别名: N-Boc-2-(tri-n-butylstannyl)piperidine；N-Boc-2-(tributylstannyl)piperidine
• CAS: 123387-55-3；1000075-49-9；1078727-67-9
• 化学式: C₂₂H₄₅NO₂Sn
• 分子量: 474.315
• InChiKey: NONKIGRXZHEOCP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.16
• 重原子数：
  26
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-t-butoxycarbonyl-2-tributylstannylpiperidine 在 吡啶 、 N-溴代丁二酰亚胺(NBS) 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 76.5h， 生成 2-isopropoxy-1-methoxy-3-phenyl-6,7,8,9-tetrahydroquinolizin-4-one
  参考文献：
  名称：

  Cyclobutenedione-Based Method for the Synthesis of Substituted 2-Pyridinones and Dihydro-2-pyridinones

  摘要：

  1,2-Addition of N-Boc-protected alpha-amino carbanions to cyclobutenediones followed by methylation of the resulting alkoxides generated 4-(1-N-Boc-aminoalkyl)-4-methoxy-3-cyclobutenones. Removal of the Boc protecting group and thermal ring expansion gave dihydro-2-pyridinones in good yields. Treatment of the dihydro-2-pyridinones with NBS/pyridine led to the formation of the corresponding 2-pyridinones. This methodology proved general with regard to both the cyclobutenediones and alpha-amino carbanions.

  DOI：

  10.1021/jo990069t
• 作为产物：
  描述：

  1-Boc-哌啶 、 三丁基氯化锡 在 四甲基乙二胺 、 仲丁基锂 作用下， 以 正己烷 、 二丁醚 为溶剂， 生成 1-t-butoxycarbonyl-2-tributylstannylpiperidine
  参考文献：
  名称：

  光氧化还原镍催化 Stille 交叉偶联反应

  摘要：

  首次设计了一种新型光氧化还原/镍催化立体收敛Stille反应，可以构建丰富的C( sp 3 )−C( sp 3 )、C( sp 3 )−C( sp 2 )、 C( sp 3 )−C( sp ) 在极其温和的条件下以良好至高的产率以优异的立体选择性键合。协同光氧化还原/镍催化的创新应用实现了锡烷试剂的新型单电子金属转移过程，为 Stille 反应领域提供了新的研究范式。

  DOI：

  10.1002/anie.202314832

文献信息

• Asymmetric Substitutions of 2-Lithiated N-Boc-piperidine and N-Boc-azepine by Dynamic Resolution
  作者：Iain Coldham、Sophie Raimbault、David T. E. Whittaker、Praful T. Chovatia、Daniele Leonori、Jignesh J. Patel、Nadeem S. Sheikh

  DOI：10.1002/chem.200903059

  日期：2010.4.6

  (N‐Boc‐piperidine) with sBuLi and TMEDA provides a racemic organolithium that can be resolved using a chiral ligand. The enantiomeric organolithiums can interconvert so that a dynamic resolution occurs. Two mechanisms for promoting enantioselectivity in the products are possible. Slow addition of an electrophile such as trimethylsilyl chloride allows dynamic resolution under kinetic control (DKR). This

  的质子抽象ñ -叔丁氧羰基哌啶（Ñ -Boc哌啶）与小号BuLi和TMEDA提供可以使用手性配体拆分的外消旋有机锂。对映体有机锂可以互变，从而产生动态拆分。促进产物中对​​映选择性的两种机制是可能的。缓慢添加亲电子试剂（例如三甲基甲硅烷基氯）可以在动力学控制（DKR）下实现动态拆分。该过程具有高对映选择性，并通过亚化学计量的手性配体催化（催化动态动力学拆分）而成功。或者，可以在热力学控制下以良好的对映选择性（动态热力学分辨率，DTR）拆分该有机锂的两种对映异构体。发现的最佳配体是基于手性二氨基醇盐。使用DTR，多种亲电试剂可用于提供对映体富集的2-取代哌啶的不对称合成，包括（在Boc脱保护后）生物碱（+）-β-羟基。尽管收率较低，但化学反应扩展到了相应的2位取代的7元氮杂环庚烷环衍生物。
• Dynamic kinetic and kinetic resolution of N-Boc-2-lithiopiperidine
  作者：Iain Coldham、Jignesh J. Patel、Sophie Raimbault、David T. E. Whittaker

  DOI：10.1039/b710066c

  日期：——

  Asymmetric substitution of 2-lithiopiperidines can be achieved by dynamic resolution; the organolithium is formed as a racemic mixture by proton abstraction (or tin–lithium exchange) and is resolved in the presence of a chiral ligand.

  2-硫代哌啶的不对称取代可以通过动态解析来实现；通过质子抽取（或锡锂交换）形成外消旋混合物的有机锂，并在手性配体存在的情况下进行解析。
• Oxidative Generation of<i>N</i>-Acyliminium Ions from<i>N</i>-1-(Tributylstannyl)alkyl Carboxamides and Carbamates and Their Reactions with Carbon Nucleophiles
  作者：Koichi Narasaka、Yasushi Kohno

  DOI：10.1246/bcsj.66.3456

  日期：1993.11

  carboxamides and carbamates with ammonium hexanitratocerate(IV) or ferrocenium hexafluorophosphate generates their N-acyliminium ions by the elimination of tributylstannyl radical under mild reaction conditions. The iminium ions thus formed react with various carbon nucleophiles to give the corresponding addition products.

  N-1-(三丁基甲锡烷基) 烷基甲酰胺和氨基甲酸酯与六硝基乙酸铵 (IV) 或二茂铁六氟磷酸酯的氧化在温和的反应条件下通过消除三丁基甲锡烷基自由基产生它们的 N-acyliminium 离子。由此形成的亚胺离子与各种碳亲核试剂反应得到相应的加成产物。
• The barrier to enantiomerization and dynamic resolution of N-Boc-2-lithiopiperidine and the effect of TMEDA
  作者：Iain Coldham、Daniele Leonori、Timothy K. Beng、Robert E. Gawley

  DOI：10.1039/b911024k

  日期：——

  The kinetics of enantiomerization and dynamic thermodynamic resolution (DTR) of N-Boc-2-lithiopiperidine have been measured, revealing significant differences in enthalpy and entropy for these processes and a role for the achiral ligand TMEDA; the racemization and the DTR are catalytic and first order in [TMEDA], and this has implications for asymmetric synthesis with chiral organolithiums.

  已经测量了 N-Boc-2-硫代哌啶的对映异构化动力学和动态热力学拆分 (DTR)，揭示了这些过程的焓和熵的显着差异以及非手性配体 TMEDA 的作用；外消旋化和 DTR 是 [TMEDA] 中的催化和一级反应，这对手性有机锂的不对称合成有影响。
• .alpha.-Lithioamine synthetic equivalents: syntheses of diastereoisomers from Boc derivatives of cyclic amines
  作者：Peter Beak、Won Koo Lee

  DOI：10.1021/jo00057a024

  日期：1993.2

  Sequences of alpha'-lithiations and electrophilic substitutions of Boc-pyrrolidines, Boc-piperidines, and Boc-hexahydroazepines that provide compounds which are substituted adjacent to nitrogen are reported, and the pathways of the reactions are discussed. By this methodology monosubstituted 2 and disubstituted 2,4,2,6, and 2,5 Boc-piperidines are obtained as single or separable diastereoisomers consistent with equatorial lithiations and retentive electrophilic substitution in chair conformations. Both cis and trans 2,6-disubstituted diastereoisomers can be prepared, and control of diastereoselectivity is demonstrated by syntheses of solenopsin A, a 2,6-trans-disubstituted piperidine, and of Boc-dihydropinidine, a 2,6-cis-disubstituted piperidine. In the case of 3-methoxy-Boc-piperidine elimination of methoxide occurs upon lithiation, and with cis-2,4-disubstituted Boc-piperidines the electrophile is introduced with trans stereochemistry at C-6. These reactions are suggested to involve twist boat conformations consistent with an X-ray crystal structure of 2-methyl-6-(trimethylstannyl)-4-phenyl-N-Boc-piperidine. Boc-pyrrolidine lithiates more rapidly than Boc-piperidine, provides 2-substituted products with electrophiles, and on further lithiation-substitution gives 2,5-cis- and -trans-substituted products. Boc-perhydroazepine provides 2-substituted products by the sequence and on further lithiation-substitution gives 2,7-trans-disubstituted products.