3-methyl-1-pentyn-3-yl methanesulphonate | 59967-07-6

• 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: 3-methyl-1-pentyn-3-yl methanesulphonate
• 英文别名: 1-Pentyn-3-ol, 3-methyl-, 3-methanesulfonate；3-methylpent-1-yn-3-yl methanesulfonate
• CAS: 59967-07-6
• 化学式: C₇H₁₂O₃S
• 分子量: 176.236
• InChiKey: FSTYDFNXJRUMRN-UHFFFAOYSA-N

物化性质

• 沸点：
  267.5±23.0 °C(Predicted)
• 密度：
  1.134±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-methyl-1-pentyn-3-yl methanesulphonate 在 Li⁽¹⁺⁾*Br₃Cu₂H^(1-) 、 copper(I) bromide 作用下， 以 四氢呋喃 为溶剂， 反应 2.58h， 生成 (3-methylpenta-1,2-dien-1-yl)benzene
  参考文献：
  名称：

  Direct Determination of the Enantiomeric Purity of Chiral Trisubstituted Allenes by Using Permethylated Cyclodextrin as a Chiral Solvating Agent

  摘要：

  The heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TRIMEB) has been successfully used as convenient chiral solvating agent to determine the enantiomeric composition of chiral trisubstituted allenes by H-1 NMR spectroscopy: the analysis of the effect of the molar ratio TRIMEB/allene, temperature, and nature of the solvent allowed us to optimize the experimental conditions to enhance the separation between the signals of the two enantiomers of each allene.

  DOI：

  10.1021/jo00083a026
• 作为产物：
  描述：

  酞己炔酯 在 氢氧化钾 、 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 3-methyl-1-pentyn-3-yl methanesulphonate
  参考文献：
  名称：

  Stoichiometric cyclotrimerisation of chiral alkynes at a ruthenium centre: preparation of optically active (η6-arene)(η4-cycloocta-1,5-diene)ruthenium(0) complexes

  摘要：

  The chiral alkynes (S)-MeCH(R)-C drop CH. 2 (R = Et, 3-methyl-1-pentyne, a; 'Pr, 3,4-dimethyl-1-pentyne, b;'Bu, 3,4,4-trimethyl-1-pentyne, c), containing a stereogenic centre in alpha position to the triple bond, react at room temperature with the complex Ru(eta (6)-naphthalene)(eta (4)-COD). 1. to give the corresponding optically active complexes Ru (eta (6)-(S)-1, 3, 5-C6H3[CH(Me)R](3)} (eta (4)-COD), 6, and Ru(eta (6)-(S)-1,2,4-C6H3[CH(Me)R](3)}(eta (4)-COD), 7. the eta (6)-1.3.5-arene regioisomer being the prevalent product. With (S)-2a, a mixture of 6a and 7a (6a/7a = 90:10) is obtained and, with the more sterically demanding alkynes (S)-2b and (S)-2c, the regioselectivity to the corresponding complexes 6b and 6c is almost complete. This synthetic procedure does not involve the stereogenic centres on the alkynes and it proceeds with complete stereoselectivity. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00881-0

文献信息

• Highly Stereoselective Palladium-Catalyzed Dithiocarbonylation of Propargylic Mesylates with Thiols and Carbon Monoxide
  作者：Wen-Jing Xiao、Howard Alper

  DOI：10.1021/jo047938l

  日期：2005.3.1

  propargylic mesylates with thiols and carbon monoxide has been developed by the use of tetrakis(triphenylphosphine)palladium(0) as the catalyst at 90 °C in THF. The reaction affords the corresponding dithioesters in good to excellent yields. For some secondary and tertiary propargylic alcohols with a terminal or internal triple bond, the reaction stereoselectively produces E-dithioesters as products. The dithiocarbonylation

  丙炔基甲磺酸酯与巯基和一氧化碳的高度立体选择性二硫羰基化反应已通过使用四（三苯基膦）钯（0）​​作为催化剂在90°C的THF中进行开发。该反应以良好至优异的产率提供了相应的二硫酯。对于某些具有末端或内部三键的仲和叔炔丙醇，该反应立体选择性地产生作为产物的E-二硫酯。据信二硫羰基化反应是通过烯丙基钯和烯丙基酯中间体进行的，并且高立体选择性可以通过一种机理来合理化，其中Pd（0）L n物质对烯丙基sp碳的亲核攻击是从烷基取代基的较少受阻侧发生的。
• Enantiocontrolled Synthesis of 3-Pyrrolines fromα-Amino Allenes
  作者：Attila Horváth、Jessica Benner、Jan-E. Bäckvall

  DOI：10.1002/ejoc.200400211

  日期：2004.8

  three novel palladium(II)-catalyzed reactions of allenes with lithium bromide and a bromonium ion induced cyclization of allenyl amides to pyrrolines. In Paper I a 1,2-functionalization of allenes is presented where bromide adds as a first nucleophile followed by intramolecular attack by an oxygen or nitrogen nucleophile. Chapter 2 deals with the extension of this reaction to different nitrogen nucleophiles

  本论文基于丙二烯与溴化锂的三种新型钯 (II) 催化反应和溴离子诱导丙二烯酰胺环化为吡咯啉。在论文 I 中，介绍了丙二烯的 1,2-官能化，其中溴化物作为第一个亲核试剂加入，然后由氧或氮亲核试剂进行分子内攻击。第 2 章涉及将该反应扩展到不同的含氮亲核试剂，如尿素、氨基甲酸酯和 N-甲苯磺酰基氨基甲酸酯，从而在温和的反应条件下以良好的产率获得取代的吡咯烷和恶唑烷。论文 II 涉及立体收敛剂钯 (II) -催化 α-乙酰氧基丙二烯与溴化物作为亲核试剂的 SN2' 反应。在该反应中，取代的 (Z,E)-2-bromo-1,3-二烯以良好的收率和优异的非对映选择性产生。论文 III 描述了手性丙二烯的温和外消旋反应。检查分子中存在的官能团对反应速率的影响。论文 I-III 中发表的所有这些反应都通过一个常见的中间体进行：2-溴-（π-烯丙基）钯配合物。第四篇论文描述了 N-保护的 α-烯丙基胺与
• Caporusso, Anna Maria; Zoppi, Alessandra; Settimo, Federico Da, Gazzetta Chimica Italiana, 1985, vol. 115, # 5, p. 293 - 296
  作者：Caporusso, Anna Maria、Zoppi, Alessandra、Settimo, Federico Da、Lardicci, Luciano

  DOI：——

  日期：——
• Direct Determination of the Enantiomeric Purity of Chiral Trisubstituted Allenes by Using Permethylated Cyclodextrin as a Chiral Solvating Agent
  作者：Gloria Uccello-Barretta、Federica Balzano、Anna Maria Caporusso、Piero Salvadori

  DOI：10.1021/jo00083a026

  日期：1994.2

  The heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TRIMEB) has been successfully used as convenient chiral solvating agent to determine the enantiomeric composition of chiral trisubstituted allenes by H-1 NMR spectroscopy: the analysis of the effect of the molar ratio TRIMEB/allene, temperature, and nature of the solvent allowed us to optimize the experimental conditions to enhance the separation between the signals of the two enantiomers of each allene.
• Stoichiometric cyclotrimerisation of chiral alkynes at a ruthenium centre: preparation of optically active (η6-arene)(η4-cycloocta-1,5-diene)ruthenium(0) complexes
  作者：Paolo Pertici、Alessandra Verrazzani、Emanuela Pitzalis、Anna Maria Caporusso、Giovanni Vitulli

  DOI：10.1016/s0022-328x(00)00881-0

  日期：2001.3

  The chiral alkynes (S)-MeCH(R)-C drop CH. 2 (R = Et, 3-methyl-1-pentyne, a; 'Pr, 3,4-dimethyl-1-pentyne, b;'Bu, 3,4,4-trimethyl-1-pentyne, c), containing a stereogenic centre in alpha position to the triple bond, react at room temperature with the complex Ru(eta (6)-naphthalene)(eta (4)-COD). 1. to give the corresponding optically active complexes Ru (eta (6)-(S)-1, 3, 5-C6H3[CH(Me)R](3)} (eta (4)-COD), 6, and Ru(eta (6)-(S)-1,2,4-C6H3[CH(Me)R](3)}(eta (4)-COD), 7. the eta (6)-1.3.5-arene regioisomer being the prevalent product. With (S)-2a, a mixture of 6a and 7a (6a/7a = 90:10) is obtained and, with the more sterically demanding alkynes (S)-2b and (S)-2c, the regioselectivity to the corresponding complexes 6b and 6c is almost complete. This synthetic procedure does not involve the stereogenic centres on the alkynes and it proceeds with complete stereoselectivity. (C) 2001 Elsevier Science B.V. All rights reserved.