1-Boc-2-三甲基锡哌啶 | 123387-54-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 中文名称: 1-Boc-2-三甲基锡哌啶
• 英文名称: N-Boc-2-trimethylsilylpiperidine
• 英文别名: 1-Boc-2-trimethylsilanylpiperidine；tert-butyl 2-trimethylsilylpiperidine-1-carboxylate
• CAS: 123387-54-2
• 化学式: C₁₃H₂₇NO₂Si
• 分子量: 257.448
• InChiKey: BSZHRPQJZZLGMD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.65
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 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-Boc-2-三甲基锡哌啶 在 lithium hydroxide 、 四甲基乙二胺 、 仲丁基锂 、 silver fluoride 、 sodium cyanoborohydride 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 溶剂黄146 、 乙腈 为溶剂， 反应 7.75h， 生成 (1S,5R,6S)-8-Methyl-8-aza-bicyclo[3.2.1]octane-6-carboxylic acid
  参考文献：
  名称：

  X-氮杂双环[ m .2.1]烷烃的立体选择性构建，其是通过[3 + 2]-环加成的非稳定的环状偶氮甲啶进行的：对映体受约束的氨基酸的合成和旋光的依巴替丁的正式全合成

  摘要：

  X-氮杂双环[ m .2.1]烷烃的立体选择性结构的一种新的通用策略是通过将环偶氮甲酰亚胺的[3 + 2]-环加成与合适的非手性偶极亲和剂开发出来的。环状的偶氮甲亚胺基团，整个内立德共轭都在环中，是通过利用Ag（I）F作为一个基团对N-烷基-α，α'-双（三甲基甲硅烷基）环状胺进行连续的双甲硅烷基化反应而生成的电子氧化剂。环状偶氮甲亚胺基化物的结构刚度允许其被双极亲和性分子优先区分出面部，从而导致非常好的外切/内切选择性。在外型/内通过与Oppolzer的丙烯酰基双极性亲和剂进行环加成反应，可以进一步开发与这些环加成反应相关的选择性，从而获得光学纯的X-氮杂双环[ m .2.1]烷烃。该方法的应用通过构建与氮杂双环结构框架有关的受约束氨基酸以及旋光表艾替巴定的正式全合成来证明。

  DOI：

  10.1016/s0040-4020(02)00322-8
• 作为产物：
  描述：

  肼基甲酸叔丁酯 在 四甲基乙二胺 、 仲丁基锂 、 溶剂黄146 、 三乙胺 、 sodium nitrite 作用下， 以 1,4-二氧六环 、 乙醚 为溶剂， 反应 33.5h， 生成 1-Boc-2-三甲基锡哌啶
  参考文献：
  名称：

  Stereoselectivity in the photoinduced electron transfer (PET) promoted intramolecular cyclisations of 1-alkenyl-2-silyl-piperidines and -pyrrolidines: rapid construction of 1-azabicyclo[m.n.0]alkanes and stereoselective synthesis of (±)-isoretronecanol and (±)-epilupinine

  摘要：

  PET promoted cyclisations of 1-alkenyl-2-silyl-pyrrolidines and -piperidines 9a-d to 1-aza-bicyclo[m.n.0]alkanes have been found to be stereoselective. The five-membered ring formation gives predominantly cis products while six-membered rings are trans. Application of such cyclisations to the synthesis of (+/-)-isoretronecanol 22a, (+/-)-epilupinine 29 and related alkaloids has been demonstrated.

  DOI：

  10.1039/p19960000219

文献信息

• [3 + 2] Cycloaddition of Nonstabilized Azomethine Ylides. 7. Stereoselective Synthesis of Epibatidine and Analogues^,
  作者：Ganesh Pandey、Trusar D. Bagul、Akhil K. Sahoo

  DOI：10.1021/jo971728+

  日期：1998.2.1

  Epibatidine (1) is synthesized by employing a [3 + 2] cycloaddition strategy as a key step via nonstabilized azomethine ylide 10, generated by one-electron oxidative double desilylation of N-benzyl-2,5-bis(trimethylsilyl)pyrrolidine (12). Cycloaddition of 10 with trans-ethyl-3-(6-chloro-3-pyridyl)-2-propenoate (22a) gives 26 in which the 6-chloro-3-pyridyl moiety is endo-oriented. Decarboxylation followed

  Epibatidine（1）是通过将非稳定的偶氮甲叶立德10用作关键步骤，采用[3 + 2]环加成策略合成的，该不稳定基是由N-苄基-2,5-双（三甲基甲硅烷基）吡咯烷的单电子氧化双甲硅烷基化反应制得的（12 ）。10与反式-3-（6-氯-3-吡啶基）-2-丙酸乙酯（22a）的环加成反应得到26，其中6-氯-3-吡啶基部分是内向的。脱羧，然后脱苄基，得到非天然差向异构体30，为1。所需的环加合物33是利用顺式-乙基-（6-氯-3-吡啶基）-2立体选择性地获得的，其中6-氯-3-吡啶基部分是外向取向的。 -丙酸酯（22b）为亲极性的。通过使用KO（t）（）Bu的差向异构反应也将30转化为1。一种替代方法，涉及通过将10与丙酸乙酯环加成，将6-氯-3-碘吡啶（37）共轭加成到36，也建议用于1的立体选择性合成。通过这种策略，使用适当的双亲性亲核试剂合成了许多取代的表巴替丁（38、39、40、4
• 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。
• [3+2]-Cycloaddition of nonstabilized azomethine ylides, part 9: A general approach for the construction of X-azabicyclo[m.2.1]alkanes in optically pure form by asymmetric 1,3-dipolar cycloaddition reactions
  作者：Ganesh Pandey、Joydev K. Laha、A.K. Mohanakrishnan

  DOI：10.1016/s0040-4039(99)01258-7

  日期：1999.8

  A general strategy for the construction of X-azabicyclo[m.2.1]alkane frameworks in optically pure form is reported by the asymmetric [3+2]-cycloaddition reaction of cyclic azomethine ylides with Oppolzer's acryloyl camphor sultam.

  通过环偶氮甲亚胺与Oppolzer的丙烯酰基樟脑sultam的不对称[3 + 2]-环加成反应，报道了构建光学纯形式的X-氮杂双环[m.2.1]烷构架的一般策略。
• 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.