(R)-α-methyl-N-[3-(trimethylsilyl)-2-propynylidene]benzenemethanamine | 141039-97-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (R)-α-methyl-N-[3-(trimethylsilyl)-2-propynylidene]benzenemethanamine
• 英文别名: (E)-N-(R)-(α-methylbenzyl)-3-(trimethylsilyl)prop-2-ynaldimine
• CAS: 141039-97-6
• 化学式: C₁₄H₁₉NSi
• 分子量: 229.397
• InChiKey: YXCXGXDJLVYTNG-WDGDVPDHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  S-phenyl butanethioate 、 (R)-α-methyl-N-[3-(trimethylsilyl)-2-propynylidene]benzenemethanamine 生成 (3R,4S)-3-Ethyl-4-ethynyl-N-(R)-α-methylbenzylamino-2-azetidinone
  参考文献：
  名称：

  MORI, MIWAKO;KAGECHIKA, KATSUJI;SASAI, HIROAKI;SHIBASAKI, MASAKATSU, CHEM. EXPRESS., 4,(1989) N, C. 89-92

  摘要：

  DOI：
• 作为产物：
  描述：

  3-三甲基甲硅烷基丙炔醛 、 R(+)-alpha-甲基苄胺 在 sodium sulfate 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 (Z)-N-(R)-(α-methylbenzyl)-3-(trimethylsilyl)prop-2-ynaldimine 、 (R)-α-methyl-N-[3-(trimethylsilyl)-2-propynylidene]benzenemethanamine
  参考文献：
  名称：

  Enantioselective synthesis of 3-amino-2-azetidinones via the ester enolate - imine condensation

  摘要：

  Three approaches to the enantioselective synthesis of 3-amino-4-substituted-2-azetidinones by condensation of alpha-amino ester enolates with imines are described: (i) application of chiral ester derivatives of NN-diethylglycine; (ii) application of chiral N-(alpha-methylbenzyl)imines; and (iii) application of chiral imines derived from (2R)-2,3-O-isopropylideneglyceraldehyde. Zinc and aluminum enolates of (-)-menthyl- and (-)-bornyl NN-diethylglycine esters react with simple imines to selectively afford trans-3-(diethylamino)-2-azetidinones, but with a low chiral induction (ee 0-35%). However, reactions of the metal (Li, Zn, Al) ester enolates of (2,2,5,5-tetramethyl-1-aza-2,4-disilacyclopent-1-yl)acetic acid ethyl ester (1c) with N-(alpha-methylbenzyl)imines yield N-protected 3-amino-2-azetidinones in excellent yields and with very high diastereo- and enantioselectivities. The best results are obtained for the zinc-mediated reactions. For example, trans-(3R,4S)-1(R)-(alpha-methylbenzyl)-3-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)-4-[N-(R)-(alpha-methylbenzyl)imino]-2-azeti dineone (4a), a fully protected key intermediate (having the unnatural C-3 configuration) for the synthesis of known monobactam and bicyclic beta-lactam antibiotics, was synthesized in 91% yield with an ee of 91%. Application of chiral imines derived from acetaldehyde and propionaldehyde enable, depending on the solvent, the selective high yielding synthesis (de 60-99%; ee >95%) of any one of the four stereoisomers of 3-amino-4-alkyl-2-azetidinones, which are key intermediates for the synthesis of Aztreonam and related antibiotics. In Et2O, a weakly polar solvent, the trans isomers are formed, whereas the use of a polar THF/HMPA solvent mixture results in formation of the cis isomers. Reaction of the zinc enolate of 1c with the N-(4-methoxyphenyl)imine derivative 2i of (2R)-2,3-O-isopropylidene glyceraldehyde affords trans-(3R,4S)-3-amino-4-[(1'S)-1',2'-O-isopropylideneethyl]-2-azetidinone (10a) in excellent yield (de 86%; ee >98%), whereas reaction of the lithium enolate of 1c with the N-(trimethylsilyl)imine derivative 21 affords the cis-(3S,4S) isomer 10d (key intermediate for the synthesis of Carumonam) in good yield (de >90%; >90%). A rationale for the observed stereoselectivities in terms of highly ordered transition states is presented.

  DOI：

  10.1021/jo00040a034