N,N-Dimethyl-2-(trimethylsilyl)ethynesulfonamide

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: N,N-Dimethyl-2-(trimethylsilyl)ethynesulfonamide
• 英文别名: N,N-dimethyl-2-trimethylsilylethynesulfonamide
• 化学式: C₇H₁₅NO₂SSi
• 分子量: 205.353
• InChiKey: ISIMRTBVWXYANH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.72
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N,N-Dimethyl-2-(trimethylsilyl)ethynesulfonamide 、 2-(Azidomethyl)-4-(1-methylethyl)-1,2-benzisothiazol-3(2H)-one 1,1-dioxide 以 苯 为溶剂， 反应 144.0h， 以82%的产率得到3-(4-Isopropyl-1,1,3-trioxo-1,3-dihydro-1λ⁶-benzo[d]isothiazol-2-ylmethyl)-5-trimethylsilanyl-3H-[1,2,3]triazole-4-sulfonic acid dimethylamide
  参考文献：
  名称：

  Steric Effects on the Regioselectivity of an Azide-Alkyne Dipolar Cycloaddition Reaction: The Synthesis of Human Leukocyte Elastase Inhibitors

  摘要：

  The cycloaddition reaction of N-(azidomethyl)benzisothiazolone 4 with various electron-deficient acetylenes gave a novel series of 1,2,3-triazoles 5-15 that were prepared for testing as inhibitors of human leukocyte elastase (HLE). Steric effects controlled the reaction regioselectivity, since as the acetylene substituent size increased from hydrogen to phenyl, tert-butyl, and trimethylsilyl, the regioisomer ratios reversed. An electronic effect of silicon appears to be responsible for the formation of only one isomer with the trimethylsilyl acetylenecarboxylate and ethynyl sulfone. For example, the 5-(phenylsulfonyl)triazole 13b was the only regioisomer detected in the reaction of phenyl 2-(trimethylsilyl)ethynyl sulfone with the azide 4. The strongly electron-withdrawing sulfone exerted no control over the regioselectivity of the cycloaddition reaction in comparison to the dominating effect of the trimethylsilyl group. High pressure and water as solvent were separately shown to accelerate the rate of product formation. The structures were unambiguously assigned on the basis of an X-ray crystal structure determination and NOE difference experiments. The derivative 12a, WIN 68123, is a potent HLE inhibitor with an apparent binding constant (K-i*) of 0.38 nM.

  DOI：

  10.1021/jo00100a019
• 作为产物：
  描述：

  二甲胺基磺酰氯 、 二(三甲基甲硅烷基)乙炔 在 三氯化铝 作用下， 生成 N,N-Dimethyl-2-(trimethylsilyl)ethynesulfonamide
  参考文献：
  名称：

  Steric Effects on the Regioselectivity of an Azide-Alkyne Dipolar Cycloaddition Reaction: The Synthesis of Human Leukocyte Elastase Inhibitors

  摘要：

  The cycloaddition reaction of N-(azidomethyl)benzisothiazolone 4 with various electron-deficient acetylenes gave a novel series of 1,2,3-triazoles 5-15 that were prepared for testing as inhibitors of human leukocyte elastase (HLE). Steric effects controlled the reaction regioselectivity, since as the acetylene substituent size increased from hydrogen to phenyl, tert-butyl, and trimethylsilyl, the regioisomer ratios reversed. An electronic effect of silicon appears to be responsible for the formation of only one isomer with the trimethylsilyl acetylenecarboxylate and ethynyl sulfone. For example, the 5-(phenylsulfonyl)triazole 13b was the only regioisomer detected in the reaction of phenyl 2-(trimethylsilyl)ethynyl sulfone with the azide 4. The strongly electron-withdrawing sulfone exerted no control over the regioselectivity of the cycloaddition reaction in comparison to the dominating effect of the trimethylsilyl group. High pressure and water as solvent were separately shown to accelerate the rate of product formation. The structures were unambiguously assigned on the basis of an X-ray crystal structure determination and NOE difference experiments. The derivative 12a, WIN 68123, is a potent HLE inhibitor with an apparent binding constant (K-i*) of 0.38 nM.

  DOI：

  10.1021/jo00100a019

文献信息

• Steric Effects on the Regioselectivity of an Azide-Alkyne Dipolar Cycloaddition Reaction: The Synthesis of Human Leukocyte Elastase Inhibitors
  作者：Dennis J. Hlasta、James H. Ackerman

  DOI：10.1021/jo00100a019

  日期：1994.10

  The cycloaddition reaction of N-(azidomethyl)benzisothiazolone 4 with various electron-deficient acetylenes gave a novel series of 1,2,3-triazoles 5-15 that were prepared for testing as inhibitors of human leukocyte elastase (HLE). Steric effects controlled the reaction regioselectivity, since as the acetylene substituent size increased from hydrogen to phenyl, tert-butyl, and trimethylsilyl, the regioisomer ratios reversed. An electronic effect of silicon appears to be responsible for the formation of only one isomer with the trimethylsilyl acetylenecarboxylate and ethynyl sulfone. For example, the 5-(phenylsulfonyl)triazole 13b was the only regioisomer detected in the reaction of phenyl 2-(trimethylsilyl)ethynyl sulfone with the azide 4. The strongly electron-withdrawing sulfone exerted no control over the regioselectivity of the cycloaddition reaction in comparison to the dominating effect of the trimethylsilyl group. High pressure and water as solvent were separately shown to accelerate the rate of product formation. The structures were unambiguously assigned on the basis of an X-ray crystal structure determination and NOE difference experiments. The derivative 12a, WIN 68123, is a potent HLE inhibitor with an apparent binding constant (K-i*) of 0.38 nM.