Tert-butyl 7-trimethylsilyl-2,3-dihydroindole-1-carboxylate | 143262-13-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: Tert-butyl 7-trimethylsilyl-2,3-dihydroindole-1-carboxylate
• CAS: 143262-13-9
• 化学式: C₁₆H₂₅NO₂Si
• 分子量: 291.466
• InChiKey: XMGPIIPRXSSKHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.53
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  吲哚啉 在 四甲基乙二胺 、 仲丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 生成 Tert-butyl 7-trimethylsilyl-2,3-dihydroindole-1-carboxylate
  参考文献：
  名称：

  Directed Lithiation of 1-(tert-Butoxycarbonyl)indolines. A Convenient Route to 7-Substituted Indolines

  摘要：

  1-(tert-Butoxycarbonyl)indolines were regioselectively lithiated at 7-position with s-BuLi-TMEDA in ether or TBF at -78-degrees-C. The lithiated species were reacted with a range of electrophiles to give 7-substituted indoline derivatives.

  DOI：

  10.3987/com-92-5993

文献信息

• .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.
• Asymmetric Deprotonations:  Lithiation of <i>N</i>-(<i>tert</i>-Butoxycarbonyl)indoline with <i>sec</i>-Butyllithium/(−)-Sparteine
  作者：Kathleen M. Bertini Gross、Young M. Jun、Peter Beak

  DOI：10.1021/jo9708856

  日期：1997.10.1

  The asymmetric lithiation of N-Boc indoline (1) with s-BuLi/(-)-sparteine and subsequent substitution provides the 2-substituted N-Boc indolines 3 and 5-11 with excellent enantiomeric ratios and in variable yields. The asymmetric lithiation-substitution sequence with N-Boc-7-chloroindoline (12) provides products 13-19 with good enantiomeric ratios. Mechanistic investigation establishes that the enantioselectivities arise from an initial asymmetric deprotonation to provide the enantioenriched and configurationally stable organolithium intermediates (S)-28 and (S)-29, which react stereoselectively with electrophiles.
• Directed Lithiation of 1-(tert-Butoxycarbonyl)indolines. A Convenient Route to 7-Substituted Indolines
  作者：Masatomo Iwao、Tsukasa Kuraishi

  DOI：10.3987/com-92-5993

  日期：——

  1-(tert-Butoxycarbonyl)indolines were regioselectively lithiated at 7-position with s-BuLi-TMEDA in ether or TBF at -78-degrees-C. The lithiated species were reacted with a range of electrophiles to give 7-substituted indoline derivatives.