N-Methyl-2-(tributylstannyl)pyrrolidine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: N-Methyl-2-(tributylstannyl)pyrrolidine
• 英文别名: tributyl-[(2R)-1-methylpyrrolidin-2-yl]stannane
• 化学式: C₁₇H₃₇NSn
• 分子量: 374.197
• InChiKey: JGLWNVODPGDHHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.47
• 重原子数：
  19
• 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：

  N-Methyl-2-(tributylstannyl)pyrrolidine 在 lithium aluminium tetrahydride 、 正丁基锂 、 四甲基乙二胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.25h， 生成 N-甲基-L-脯氨醇
  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：

  二异丁基氢化铝 、 1-(t-butoxycarbonyl)-2-(tributylstannyl)pyrrolidine 以75%的产率得到N-Methyl-2-(tributylstannyl)pyrrolidine
  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

• 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。
• The Steric Course of S_E2 Reactions of Unstabilized α-Aminoorganolithiums:  Distinguishing between SET and Polar Mechanisms
  作者：Robert E. Gawley、Eddy Low、Qianhui Zhang、Roy Harris

  DOI：10.1021/ja9923235

  日期：2000.4.1

  possible pathways considered are single electron transfer (SET) and competing polar substitutions (SE2ret vs SE2inv). Catalysis of organolithium racemization by the electrophile was eliminated as a possible source of racemic products. When the products are completely racemic, our evidence suggests that SET is the most likely mechanism; when polar pathways are operative, stereoselectivities vary from 75

  比较了确定构型稳定、不稳定的 α-氨基有机锂的亲电脂肪族取代反应 (SE2) 空间过程的竞争机制。锂化吡咯烷和哌啶与亲电试剂反应的空间过程是可变的，例如在两种亲电试剂和单一有机锂之间进行比较时，或在两种有机锂和单一亲电试剂之间进行比较时。考虑的可能途径是单电子转移（SET）和竞争性极性取代（SE2ret vs SE2inv）。亲电子试剂对有机锂外消旋化的催化作用被排除为外消旋产物的可能来源。当产品完全外消旋时，我们的证据表明 SET 是最可能的机制；当极地路径有效时，
• Gawley, Robert E.; Zhang, Qianhui; Campagna, Silvio, Journal of the American Chemical Society, 1995, vol. 117, # 47, p. 11817 - 11818
  作者：Gawley, Robert E.、Zhang, Qianhui、Campagna, Silvio

  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.
• 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：——