(R)-2-Amino-but-3-yn-1-ol | 104173-33-3

• 分子结构分类: 有机化合物 - 乙炔化物 - 碳化物
• 英文名称: (R)-2-Amino-but-3-yn-1-ol
• 英文别名: (R)-2-Aminobut-3-yn-1-ol；(2R)-2-aminobut-3-yn-1-ol
• CAS: 104173-33-3
• 化学式: C₄H₇NO
• 分子量: 85.1057
• InChiKey: RSUWHQXXMTYZTI-SCSAIBSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,4,6-三甲基苯磺酰氯 、 (R)-2-Amino-but-3-yn-1-ol 在 三乙胺 作用下， 以 氯仿 为溶剂， 反应 1.5h， 以149 mg的产率得到(2R)-2-[(N-2,4,6-trimethyl-phenylsulfonyl)amino]-but-3-yn-1-ol
  参考文献：
  名称：

  A Highly cis-Selective Synthesis of 2-Ethynylaziridines by Intramolecular Amination of Chiral Bromoallenes:  Improvement of Stereoselectivity Based on the Computational Investigation

  摘要：

  The base-mediated intramolecular amination of bromoallenes having an axial chirality is described. The treatment of (4S,aR)-4-alkyl-4-[N-(arylsulfonyl)amino]-1-bromobuta-1,2-dienes with NaH in DMF affords 2,3-cis-2-ethynylaziridines in good to excellent selectivity (2,3-cis:trans = 92:8-99:1). The reaction of (4S,aS)-bromoallenes with NaH/DMF also gives 2,3-cis-2-ethynylaziridines selectively (79:21-91:9). These experimental results have been rationalized by 133LYP density functional calculations together with the 6-31 +G(d) basis set and the Onsager solvation model. The transition structures for cis-aziridine formation of both (4S,aR)- and (4S,aS)-bromoallenes in DMF are favored over the corresponding trans transition structures by 4.35 and 1.41 kcal/mol, respectively. Furthermore, the calculations predicted that a less polar solvent gives higher cis selectivity for (4S,aS)-bromoallenes. In fact, improvement of the cis selectivity to 99:1 has been realized by using a less polar solvent such as THF. The cyclization of bromoallenes bearing a beta- or gamma-amino group also affords four- and five-membered azacycles in a highly cis-selective manner.

  DOI：

  10.1021/ja0262277
• 作为产物：
  描述：

  (R)-2,2-二甲基-3-(n-boc)-4-乙炔噁唑啉 在 甲醇 、 三氟乙酸 作用下， 反应 1.5h， 生成 (R)-2-Amino-but-3-yn-1-ol
  参考文献：
  名称：

  使用溴丙二烯作为烯丙基双阳离子当量的钯 (0)-催化合成中等大小的杂环

  摘要：

  我们开发了一种高度区域选择性和立体选择性合成的中等大小杂环，通过在钯 (0) 催化剂和醇的存在下，带有氧、氮或碳亲核官能团的溴丙二烯环化。在该反应中，溴丙二烯充当烯丙基双阳离子等价物，分子内亲核攻击仅发生在丙二烯部分的中心碳原子上。有趣的是，具有五原子系链的碳亲核试剂的溴丙二烯可提供具有反式构型的八元环，而具有氧或氮亲核试剂的溴丙二烯则选择性地提供相应的顺式环。这是第一个证明通过溴丙二烯环化合成中等大小环的例子，

  DOI：

  10.1021/ja048693x

文献信息

• Synthesis of optically active β,γ-alkynylglycine derivatives
  作者：Patrick Meffre、Laurence Gauzy、Eric Branquet、Philippe Durand、François Le Goffic

  DOI：10.1016/0040-4020(96)00630-8

  日期：1996.8

  Full results on the first synthesis of optically active β,γ-alkynylglycine derivatives from naturally occurring L-serine are described. The methodology uses L-serinal as a key intermediate and allows great versatility in the introduction of N-protective groups and of alkyne substitution. The N-Boc protected β,γ-alkynylglycine derivatives described have ee greater than 90%.

  描述了从天然存在的L-丝氨酸首次合成旋光性β，γ-炔基甘氨酸衍生物的完整结果。该方法使用L-丝氨酸作为关键中间体，在引入N保护基和炔烃取代方面具有极大的通用性。所述的N-Boc保护的β，γ-炔基甘氨酸衍生物的ee大于90％。
• En route to optically active ethynylglycine derivatives
  作者：Patrick Meffre、Laurence Gauzy、Chantal Perdigues、Florence Desanges-Levecque、Eric Branquet、Philippe Durand、François Le Goffic

  DOI：10.1016/0040-4039(94)02384-n

  日期：1995.2

  First results in the synthesis of chiral non racemic ethynylglycine derivatives from protected L-serinal are described.

  描述了从受保护的L-丝氨酸合成手性非外消旋乙炔基甘氨酸衍生物的第一个结果。
• Renaud, Philippe; Seebach, Dieter, Angewandte Chemie, 1986, vol. 98, # 9, p. 836 - 838
  作者：Renaud, Philippe、Seebach, Dieter

  DOI：——

  日期：——
• A Highly <i>cis</i>-Selective Synthesis of 2-Ethynylaziridines by Intramolecular Amination of Chiral Bromoallenes:  Improvement of Stereoselectivity Based on the Computational Investigation
  作者：Hiroaki Ohno、Kaori Ando、Hisao Hamaguchi、Yusuke Takeoka、Tetsuaki Tanaka

  DOI：10.1021/ja0262277

  日期：2002.12.1

  The base-mediated intramolecular amination of bromoallenes having an axial chirality is described. The treatment of (4S,aR)-4-alkyl-4-[N-(arylsulfonyl)amino]-1-bromobuta-1,2-dienes with NaH in DMF affords 2,3-cis-2-ethynylaziridines in good to excellent selectivity (2,3-cis:trans = 92:8-99:1). The reaction of (4S,aS)-bromoallenes with NaH/DMF also gives 2,3-cis-2-ethynylaziridines selectively (79:21-91:9). These experimental results have been rationalized by 133LYP density functional calculations together with the 6-31 +G(d) basis set and the Onsager solvation model. The transition structures for cis-aziridine formation of both (4S,aR)- and (4S,aS)-bromoallenes in DMF are favored over the corresponding trans transition structures by 4.35 and 1.41 kcal/mol, respectively. Furthermore, the calculations predicted that a less polar solvent gives higher cis selectivity for (4S,aS)-bromoallenes. In fact, improvement of the cis selectivity to 99:1 has been realized by using a less polar solvent such as THF. The cyclization of bromoallenes bearing a beta- or gamma-amino group also affords four- and five-membered azacycles in a highly cis-selective manner.
• Palladium(0)-Catalyzed Synthesis of Medium-Sized Heterocycles by Using Bromoallenes as an Allyl Dication Equivalent
  作者：Hiroaki Ohno、Hisao Hamaguchi、Miyo Ohata、Shohei Kosaka、Tetsuaki Tanaka

  DOI：10.1021/ja048693x

  日期：2004.7.1

  We have developed a highly regio- and stereoselective synthesis of medium-sized heterocycles containing one or two heteroatoms via cyclization of bromoallenes bearing an oxygen, nitrogen, or carbon nucleophilic functionality in the presence of a palladium(0) catalyst and alcohol. In this reaction, bromoallenes act as an allyl dication equivalent, and the intramolecular nucleophilic attack takes place

  我们开发了一种高度区域选择性和立体选择性合成的中等大小杂环，通过在钯 (0) 催化剂和醇的存在下，带有氧、氮或碳亲核官能团的溴丙二烯环化。在该反应中，溴丙二烯充当烯丙基双阳离子等价物，分子内亲核攻击仅发生在丙二烯部分的中心碳原子上。有趣的是，具有五原子系链的碳亲核试剂的溴丙二烯可提供具有反式构型的八元环，而具有氧或氮亲核试剂的溴丙二烯则选择性地提供相应的顺式环。这是第一个证明通过溴丙二烯环化合成中等大小环的例子，