(R)-N-Methyl-2-(tributylstannyl)piperidine | 150130-31-7

• 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: (R)-N-Methyl-2-(tributylstannyl)piperidine
• CAS: 150130-31-7
• 化学式: C₁₈H₃₉NSn
• 分子量: 388.224
• InChiKey: SNXROJZXWGDCLZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.86
• 重原子数：
  20
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-N-Methyl-2-(tributylstannyl)piperidine 在 lithium aluminium tetrahydride 、 正丁基锂 、 四甲基乙二胺 作用下， 以 乙醚 为溶剂， 反应 3.33h， 生成 (2S)-N-甲基-2-哌啶甲醇
  参考文献：
  名称：

  Alkylation of 2-lithio-N-methylpiperidines and -pyrrolidines: scope, limitations, and stereochemistry

  摘要：

  The scope and limitations of the alkylation of racemic and nonracemic 2-lithiopiperidines and -pyrrolidines, obtained by transmetalation of the corresponding stannanes, is reported. These organolithiums react with a variety of electrophiles to afford 2-substituted pyrrolidines and piperidines in excellent yield. With primary alkyl halides the reaction proceeds with net inversion of configuration at the metal-bearing carbon in the piperidines; in the pyrrolidines there is a mixture of inversion and retention, with the former predominating. With most carbonyl electrophiles (carbon dioxide, dimethyl carbonate, methyl chloroformate, pivaloyl chloride, benzaldehyde, and dialkyl ketones), retention is observed in both cases. Electrophiles such as benzophenone, benzyl bromide, and tert-butyl bromoacetate afford racemic coupling products. A mechanistic interpretation is presented.

  DOI：

  10.1021/jo00123a008
• 作为产物：
  描述：

  甲乙酐 、 tributyl-[(2R)-1-[(4S)-4-propan-2-yl-4,5-dihydro-1,3-oxazol-2-yl]piperidin-2-yl]stannane 、 lithium aluminium tetrahydride 生成 (R)-N-Methyl-2-(tributylstannyl)piperidine 、 (R)-N-Methyl-2-(tributylstannyl)piperidine
  参考文献：
  名称：

  Gawley, Robert E.; Zhang, Qianhui, Journal of the American Chemical Society, 1993, vol. 115, # 16, p. 7515 - 7516

  摘要：

  DOI：

文献信息

• Stereoselective [2,3]-Sigmatropic Rearrangements of Unstabilized Nitrogen Ylides
  作者：Robert E. Gawley、Kwangyul Moon

  DOI：10.1021/ol071188v

  日期：2007.8.1

  The steric course of the [2,3]-rearrangement of several unstabilized nitrogen ylides has been investigated. The reactions proceed cleanly through an anti transition state, affording modest to good yields of a single diastereomer of the product. In two examples containing an N-cinnamyl group, a competing [1,2]-rearrangement affords a minor product.

  已经研究了几种不稳定的氮基[2,3]重排的空间过程。反应通过反过渡态进行，使产物的单一非对映异构体收率适中，收率良好。在含有N-肉桂基的两个实例中，竞争的[1,2]重排提供了次要产物。
• Search for configurationally stable, aracemic α-amino organolithiums
  作者：Robert E. Gawley、Qianhui Zhang

  DOI：10.1016/s0040-4020(01)90459-4

  日期：1994.1

  search for configurationally stable α-amino carbanions has led to an interesting observation of differing reactivity of diastereomeric organolithiums and to the characterization of aracemic 2-lithio-N-methylpiperidine and 2-lithio-N-methylpyrrolidine as configurationally stable α-aminoorganolithiums. Details for the preparation of these and related α-lithioheterocycles, evaluation of their chemical and configurational

  对构型稳定的α-氨基碳负离子的研究导致了对非对映异构有机锂的不同反应性的有趣观察，并导致了无规2-硫代-N-甲基哌啶和2-硫代-N-甲基吡咯烷表征为构型稳定的α-氨基有机锂。提供了这些和相关的α-硫代杂环的制备，化学和构型稳定性评估以及它们与亲电试剂反应的立体选择性的初步评估的详细信息。
• Gawley, Robert E.; Zhang, Qianhui, Journal of the American Chemical Society, 1993, vol. 115, # 16, p. 7515 - 7516
  作者：Gawley, Robert E.、Zhang, Qianhui

  DOI：——

  日期：——
• Alkylation of 2-lithio-N-methylpiperidines and -pyrrolidines: scope, limitations, and stereochemistry
  作者：Robert E. Gawley、Qianhui Zhang

  DOI：10.1021/jo00123a008

  日期：1995.9

  The scope and limitations of the alkylation of racemic and nonracemic 2-lithiopiperidines and -pyrrolidines, obtained by transmetalation of the corresponding stannanes, is reported. These organolithiums react with a variety of electrophiles to afford 2-substituted pyrrolidines and piperidines in excellent yield. With primary alkyl halides the reaction proceeds with net inversion of configuration at the metal-bearing carbon in the piperidines; in the pyrrolidines there is a mixture of inversion and retention, with the former predominating. With most carbonyl electrophiles (carbon dioxide, dimethyl carbonate, methyl chloroformate, pivaloyl chloride, benzaldehyde, and dialkyl ketones), retention is observed in both cases. Electrophiles such as benzophenone, benzyl bromide, and tert-butyl bromoacetate afford racemic coupling products. A mechanistic interpretation is presented.