(+)-N,O-bis(triisopropylsilyl)-L-methionine | 1006035-40-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (+)-N,O-bis(triisopropylsilyl)-L-methionine
• 英文别名: tri(propan-2-yl)silyl (2S)-4-methylsulfanyl-2-[tri(propan-2-yl)silylamino]butanoate
• CAS: 1006035-40-0
• 化学式: C₂₃H₅₁NO₂SSi₂
• 分子量: 461.9
• InChiKey: VQWVEQXBSLFOPY-QFIPXVFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.59
• 重原子数：
  29
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+)-N,O-bis(triisopropylsilyl)-L-methionine 在 dimethyl sulfide borane 作用下， 反应 2.0h， 生成 (4S,5S)-4-(2-methylsulfanylethyl)-3-(triisopropylsilyl)-5-(triisopropylsilyloxy)-1,3,2-oxazaborolidine 、 (4S,5R)-4-(2-methylsulfanylethyl)-3-(triisopropylsilyl)-5-(triisopropylsilyloxy)-1,3,2-oxazaborolidine
  参考文献：
  名称：

  Enantiomerically Pure α-Amino Aldehydes from Silylated α-Amino Acids

  摘要：

  The disilylation of alpha-amino acids 1 to provide 2 (72-87%) was achieved without racemization. An unprecedented borane-mediated semi-reduction strategy was devised to convert 2 to stable, isolable oxazaborolidines 3 (100%) which were hydrolyzed to provide 5 (49-60%) as pure, stable compounds. Analysis of the Mosher amides (8) of the gamma-amino esters 7 reveals that <= 2% racemization occurs in the 1 -> 8 conversions.

  DOI：

  10.1021/ol7028993
• 作为产物：
  描述：

  L-蛋氨酸 、 三异丙基硅基三氟甲磺酸酯 在 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 以72%的产率得到(+)-N,O-bis(triisopropylsilyl)-L-methionine
  参考文献：
  名称：

  Selective Triisopropylsilylation of α-Amino Acids: Protection without Racemization

  摘要：

  The mono-, di- and trisilylation of alpha-amino acids with TIPSOTf is described. Treatment of the alpha-amino acids, proline and tryptophan with TIPSOTf in MeCN provides a quantitative yield of the corresponding ammonium salts of the O-TIPS esters (4). Employing two (2) equivalents of TIPSOTf/EDIPA produces N,O-bis-TIPS amino acid derivatives (2) without racemization as stable compounds (73-87%, 13 examples). Three (3) equivalents of this silylation mixture produces the corresponding tris-TIPS derivatives 6 (62-88%, 6 examples) from amino acids which contain protic functionality in their side chain. While this trisilylation procedure is ineffective for tryptophan, the N,O-bis-TIPS derivative 2m is easily prepared through this method, and the third silylation is achieved without racemization employing t-BuLi/R3SiX producing N-1-SiR3-N,O-bis-TIPS tryptophans (51-97%, 4 examples).

  DOI：

  10.3987/com-09-s(s)37

文献信息

• Selective Triisopropylsilylation of α-Amino Acids: Protection without Racemization
  作者：John A. Soderquist、Buddy Soto-Cairoli、Iveliz Kock、Guang Yang、Jorge Justo de Pomar、José M. Guzmán、Javier R. González、Augie Antomattei

  DOI：10.3987/com-09-s(s)37

  日期：——

  The mono-, di- and trisilylation of alpha-amino acids with TIPSOTf is described. Treatment of the alpha-amino acids, proline and tryptophan with TIPSOTf in MeCN provides a quantitative yield of the corresponding ammonium salts of the O-TIPS esters (4). Employing two (2) equivalents of TIPSOTf/EDIPA produces N,O-bis-TIPS amino acid derivatives (2) without racemization as stable compounds (73-87%, 13 examples). Three (3) equivalents of this silylation mixture produces the corresponding tris-TIPS derivatives 6 (62-88%, 6 examples) from amino acids which contain protic functionality in their side chain. While this trisilylation procedure is ineffective for tryptophan, the N,O-bis-TIPS derivative 2m is easily prepared through this method, and the third silylation is achieved without racemization employing t-BuLi/R3SiX producing N-1-SiR3-N,O-bis-TIPS tryptophans (51-97%, 4 examples).
• Enantiomerically Pure α-Amino Aldehydes from Silylated α-Amino Acids
  作者：Buddy Soto-Cairoli、Jorge Justo de Pomar、John A. Soderquist

  DOI：10.1021/ol7028993

  日期：2008.1.1

  The disilylation of alpha-amino acids 1 to provide 2 (72-87%) was achieved without racemization. An unprecedented borane-mediated semi-reduction strategy was devised to convert 2 to stable, isolable oxazaborolidines 3 (100%) which were hydrolyzed to provide 5 (49-60%) as pure, stable compounds. Analysis of the Mosher amides (8) of the gamma-amino esters 7 reveals that <= 2% racemization occurs in the 1 -> 8 conversions.