(S)-N-Boc-5-(1-amino-3-methyl-butyl)-2,2,8,8-tetramethylnona-3,6-diyn-5-ol | 1371568-39-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-N-Boc-5-(1-amino-3-methyl-butyl)-2,2,8,8-tetramethylnona-3,6-diyn-5-ol
• 英文别名: tert-butyl N-[(4S)-5-(3,3-dimethylbut-1-ynyl)-5-hydroxy-2,8,8-trimethylnon-6-yn-4-yl]carbamate
• CAS: 1371568-39-6
• 化学式: C₂₃H₃₉NO₃
• 分子量: 377.568
• InChiKey: QKYYWSRYTMQHDV-SFHVURJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  27
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-N-Boc-5-(1-amino-3-methyl-butyl)-2,2,8,8-tetramethylnona-3,6-diyn-5-ol 在 二氧化碳 、 水 、 对甲苯磺酸 、 copper dichloride 作用下， 以 甲醇 为溶剂， 100.0 ℃ 、4.05 MPa 条件下， 反应 15.0h， 以78%的产率得到1-(5-tert-butyl-2-isobutyl-1H-pyrrol-3-yl)-3,3-dimethylbutan-1-one
  参考文献：
  名称：

  Copper-Catalyzed Synthesis of Substituted Furans and Pyrroles by Heterocyclodehydration and Tandem Heterocyclodehydration–Hydration of 3-Yne-1,2-diols and 1-Amino-3-yn-2-ol Derivatives

  摘要：

  CuCl2-catalyzed heterocyclodehydration of readily available 3-yne-1,2-diols and 1-amino-3-yn-2-ol derivatives afforded substituted furans and pyrroles, respectively, in good to high yields (53-99%) under mild conditions (MeOH as the solvent, 80-100 degrees C, 1-24 h). In the case of 2,2-dialkynyl-1,2-diols, bearing an additional alkynyl substituent at C-2, a cascade process, corresponding to copper-catalyzed heterocyclodehydration followed by acid-catalyzed hydration of the triple bond, was realized when the reaction was carried out in the presence of both CuCl2 and TsOH, leading to 3-acylfurans in one step and high yields (75-84%). Under the same conditions, N-Boc-2-alkynyl-1-amino-3-yn-2-ols were converted into the corresponding N-unsubstituted 3-acylpyrroles in low to fair yields (19-59%). However, working in the presence of added water and a large excess of CO2 (40 atm), in addition to CuCl2 and TsOH, caused a significant improvement of the yields of 3-acylpyrroles (68-87%), thus making the method of general synthetic applicability.

  DOI：

  10.1021/jo400533j
• 作为产物：
  描述：

  3,3-二甲基-1-丁炔 、 BOC-L-亮氨酸甲酯 在 溴乙烷 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 2.25h， 以58%的产率得到(S)-N-Boc-5-(1-amino-3-methyl-butyl)-2,2,8,8-tetramethylnona-3,6-diyn-5-ol
  参考文献：
  名称：

  A Palladium Iodide-Catalyzed Carbonylative Approach to Functionalized Pyrrole Derivatives

  摘要：

  A novel and convenient approach to functionalized pyrroles is presented, based on Pd-catalyzed oxidative heterocyclization-alkoxycarbonylation of readily available N-Boc-1-amino-3-yn-2-ols. Reactions were carried out in alcoholic solvents at 80-100 degrees C and under 20 atm (at 25 degrees C) of a 4:1 mixture of CO air, in the presence of the PdI2-KI catalytic system (2-5 mol % of PdI2, KI/PdI2, molar ratio = 10). In the case of N-Boc-1-amino-3-yn-2-ols 3, bearing alkyl or aryl substituents, the carbonylation reaction led to a mixture of Boc-protected and N-unsubstituted pyrrole-3-carboxylic esters 4 and 5, respectively. This mixture could be conveniently and quantitatively converted into deprotected pyrrole-3-carboxylic esters 5 by a simple basic treatment. In the case of diastereomeric (3RS,4RS)- and (3RS,4SR)-N-Boc-3-amino-2-methyldec-5-yn-4-ol (syn-3f and anti-3f, respectively, whose relative configuration was determined by X-ray crystallographic analysis), no particular difference was observed in the reactivity of the two diastereomers between them and with respect to the diastereomeric mixture (3S,4S) + (3S,4R). Interestingly, N-Boc-2-alkynyl-1-amino-3-yn-2-ols 6, bearing an additional alkynyl substituent alpha to the hydroxyl group, spontaneously underwent N-deprotection under the reaction conditions and regioselective water addition to the alkynyl group at C-3 of the corresponding pyrrole-3-carboxylic ester derivative, thus directly affording highly functionalized pyrrole derivatives 7 in one step. In a similar manner, a novel functionalized dihydropyrrolizine derivative 9 was directly synthesized starting from (S)-7-(pyrrolidin-2-yl)trideca-5,8-diyn-7-ol 8.

  DOI：

  10.1021/jo300365n

文献信息

• A Palladium Iodide-Catalyzed Carbonylative Approach to Functionalized Pyrrole Derivatives
  作者：Bartolo Gabriele、Lucia Veltri、Raffaella Mancuso、Giuseppe Salerno、Sabino Maggi、Brunella Maria Aresta

  DOI：10.1021/jo300365n

  日期：2012.4.20

  A novel and convenient approach to functionalized pyrroles is presented, based on Pd-catalyzed oxidative heterocyclization-alkoxycarbonylation of readily available N-Boc-1-amino-3-yn-2-ols. Reactions were carried out in alcoholic solvents at 80-100 degrees C and under 20 atm (at 25 degrees C) of a 4:1 mixture of CO air, in the presence of the PdI2-KI catalytic system (2-5 mol % of PdI2, KI/PdI2, molar ratio = 10). In the case of N-Boc-1-amino-3-yn-2-ols 3, bearing alkyl or aryl substituents, the carbonylation reaction led to a mixture of Boc-protected and N-unsubstituted pyrrole-3-carboxylic esters 4 and 5, respectively. This mixture could be conveniently and quantitatively converted into deprotected pyrrole-3-carboxylic esters 5 by a simple basic treatment. In the case of diastereomeric (3RS,4RS)- and (3RS,4SR)-N-Boc-3-amino-2-methyldec-5-yn-4-ol (syn-3f and anti-3f, respectively, whose relative configuration was determined by X-ray crystallographic analysis), no particular difference was observed in the reactivity of the two diastereomers between them and with respect to the diastereomeric mixture (3S,4S) + (3S,4R). Interestingly, N-Boc-2-alkynyl-1-amino-3-yn-2-ols 6, bearing an additional alkynyl substituent alpha to the hydroxyl group, spontaneously underwent N-deprotection under the reaction conditions and regioselective water addition to the alkynyl group at C-3 of the corresponding pyrrole-3-carboxylic ester derivative, thus directly affording highly functionalized pyrrole derivatives 7 in one step. In a similar manner, a novel functionalized dihydropyrrolizine derivative 9 was directly synthesized starting from (S)-7-(pyrrolidin-2-yl)trideca-5,8-diyn-7-ol 8.
• Copper-Catalyzed Synthesis of Substituted Furans and Pyrroles by Heterocyclodehydration and Tandem Heterocyclodehydration–Hydration of 3-Yne-1,2-diols and 1-Amino-3-yn-2-ol Derivatives
  作者：Bartolo Gabriele、Lucia Veltri、Pierluigi Plastina、Raffaella Mancuso、Mabel V. Vetere、Vito Maltese

  DOI：10.1021/jo400533j

  日期：2013.5.17

  CuCl2-catalyzed heterocyclodehydration of readily available 3-yne-1,2-diols and 1-amino-3-yn-2-ol derivatives afforded substituted furans and pyrroles, respectively, in good to high yields (53-99%) under mild conditions (MeOH as the solvent, 80-100 degrees C, 1-24 h). In the case of 2,2-dialkynyl-1,2-diols, bearing an additional alkynyl substituent at C-2, a cascade process, corresponding to copper-catalyzed heterocyclodehydration followed by acid-catalyzed hydration of the triple bond, was realized when the reaction was carried out in the presence of both CuCl2 and TsOH, leading to 3-acylfurans in one step and high yields (75-84%). Under the same conditions, N-Boc-2-alkynyl-1-amino-3-yn-2-ols were converted into the corresponding N-unsubstituted 3-acylpyrroles in low to fair yields (19-59%). However, working in the presence of added water and a large excess of CO2 (40 atm), in addition to CuCl2 and TsOH, caused a significant improvement of the yields of 3-acylpyrroles (68-87%), thus making the method of general synthetic applicability.