N-(3-hydroxypropyl)-4-methyl-N-(3-methylbut-2-enyl)benzenesulfonamide | 475292-74-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(3-hydroxypropyl)-4-methyl-N-(3-methylbut-2-enyl)benzenesulfonamide
• CAS: 475292-74-1
• 化学式: C₁₅H₂₃NO₃S
• 分子量: 297.419
• InChiKey: BVEBKJFGMHHONL-UHFFFAOYSA-N

物化性质

• 熔点：
  42-43 °C(Solv: hexane (110-54-3); ethyl acetate (141-78-6))
• 沸点：
  447.6±55.0 °C(Predicted)
• 密度：
  1.138±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(3-hydroxypropyl)-4-methyl-N-(3-methylbut-2-enyl)benzenesulfonamide 在 四溴化碳 、 sodium hexamethyldisilazane 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 2-[4-aza-7-methyl-4-(p-toluenesulfonyl)oct-6-enyl]malonic acid dimethyl ester
  参考文献：
  名称：

  Synthesis of 3,4-disubstituted piperidines by ene cyclisation of 4-aza-1,7-dienes

  摘要：

  Ene cyclisation of a variety of 4-aza-1,7-dienes affords 3,4-disubstituted piperidines. In particular, cyclisation of diesters 14 and 20 catalysed by MeAlCl2 gives the corresponding trans 3,4-disubstituted piperidines with diastereomeric ratios of > 200:1. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.08.002
• 作为产物：
  描述：

  3-甲基-2-丁烯酸乙酯 在 三溴化磷 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 13.0h， 生成 N-(3-hydroxypropyl)-4-methyl-N-(3-methylbut-2-enyl)benzenesulfonamide
  参考文献：
  名称：

  Visible-Light-Promoted Intramolecular α-Allylation of Aldehydes in the Absence of Sacrificial Hydrogen Acceptors

  摘要：

  We report herein an unprecedented protocol for radical cyclization of aldehydes with pendant alkenes via synergistic photoredox, cobaloxime, and amine catalysis. The transformation was achieved in the absence of external oxidants, providing a variety of 5-, 6-, and 7-membered ring products with alkene transposition in satisfactory yields. The reaction exhibits wide functional group compatibility and occurs under mild conditions with extrusion of H-2.

  DOI：

  10.1021/acs.orglett.0c02742

文献信息

• Synthesis of 3,4-Disubstituted Piperidines by Carbonyl Ene and Prins Cyclizations:  Switching between Kinetic and Thermodynamic Control with Brønsted and Lewis Acid Catalysts
  作者：Jodi T. Williams、Perdip S. Bahia、Benson M. Kariuki、Neil Spencer、Douglas Philp、John S. Snaith

  DOI：10.1021/jo052532+

  日期：2006.3.1

  to cis and trans 3,4-disubstituted piperidines is described. Carbonyl ene cyclization of aldehydes 4a−e catalyzed by MeAlCl2 in refluxing chloroform afforded the trans piperidines 7a−e with diastereomeric ratios of up to 93:7, while aldehyde 4f afforded solely the cis product 6f, which was resistant to isomerization to the trans isomer. It was demonstrated for 4a that the cyclization catalyzed by a

  描述了一种新的顺式和反式3,4-二取代哌啶方法。在回流的氯仿中，MeAlCl 2催化的醛4a - e的羰基烯环化反应提供了高达93：7的非对映异构体比例的反式哌啶7a - e，而醛4f仅提供了顺式异构体6f，对顺反异构体具有抗性异构体。对于4a，证明了在动力学控制下进行的多种路易斯酸在低温下催化的环化反应主要得到顺式哌啶6a。，并在升温时异构化为热力学上更稳定的反式哌啶7a。与此相反，环化王子4A - ë浓盐酸在CH催化2氯2在低温下，得到顺式的哌啶6A - Ë最多的非对映体比率，以> 98:2。这些环化反应的收率和非对映选择性可以通过使用HCl饱和的CH 2 Cl 2形成相应的氯化物，然后除去氨影响的HCl来改善。醛4f和4g在后一种条件下也以良好的产率环化。DFT计算（B3LYP / 6-31G（d））支持的机理研究表明，环化反应是通过具有显着碳正离子特性的机理进行的，顺式碳正离子比反
• Enantioselective Intramolecular Aldehyde α-Alkylation with Simple Olefins: Direct Access to Homo-Ene Products
  作者：Robert J. Comito、Fernanda G. Finelli、David W. C. MacMillan

  DOI：10.1021/ja4047312

  日期：2013.6.26

  A highly selective method for the synthesis of asymmetrically substituted carbocycles and heterocycles from unactivated aldehyde-olefin precursors has been achieved via enantioselective SOMO-catalysis. Addition of a catalytically generated enamine radical cation across a pendent olefin serves to establish a general asymmetric strategy toward the production of a wide range of formyl-substituted rings

  通过对映选择性 SOMO 催化，实现了一种从未活化的醛-烯烃前体合成不对称取代的碳环和杂环的高选择性方法。在悬垂烯烃上添加催化生成的烯胺自由基阳离子有助于建立一般的不对称策略，以产生广泛的具有烯烃转位的甲酰基取代的环。从概念上讲，这种新颖的机制允许直接访问“均烯”型产品。
• Stereoselective synthesis of 3,4-disubstituted and 3,4,5-trisubstituted piperidines by Lewis acid-catalysed ene cyclisation of 4-aza-1,7-dienes
  作者：Stephen M. Walker、Jodi T. Williams、Alexander G. Russell、Benson M. Kariuki、John S. Snaith

  DOI：10.1039/b708139a

  日期：——

  there was a fine balance between the desired ene cyclisation and the competing hetero-Diels-Alder reaction, with the product distribution being influenced by the activating group on the enophile, the nature of the ene component, and the Lewis acid used. Activation of the enophile with an oxazolidinone function facilitated Lewis acid-catalysed cyclisation to afford mixtures of ene and hetero-Diels-Alder

  各种4-氮杂-1，7-二烯的热或路易斯酸催化的烯环化得到3，4-二取代或3，4，5-三取代的哌啶。尽管该反应不适合路易斯酸催化，但是用单酯活化亲油体促进了热烯环化。与亲脂体上的其他活化基团一起发现路易斯酸催化很容易，尽管所需的烯环化和竞争性杂-Diels-Alder反应之间存在良好的平衡，产物分布受烯基上活化基团的影响。亲烯体，烯组分的性质以及所用的路易斯酸。具有恶唑烷酮功能的亲油体的活化促进了路易斯酸催化的环化作用，得到了烯和杂-Diels-Alder产物的混合物。
• Synthesis of 3,4-Disubstituted Piperidines by Carbonyl Ene and Prins Cyclizations:  A Switch in Diastereoselectivity between Lewis and Brønsted Acid Catalysts
  作者：Jodi T. Williams、Perdip Singh Bahia、John S. Snaith

  DOI：10.1021/ol0266929

  日期：2002.10.1

  [GRAPHIC]A novel diastereoselective approach to cis and trans 3,4-disubstituted piperidines is described. Carbonyl ene cyclization of aldehydes 6a-e catalyzed by the Lewis acid methyl aluminum dichloride in refluxing chloroform affords trans piperidines 8a-e with diastereomeric ratios of up to 93:7. By contrast, Prins cyclization of 6a-e catalyzed by hydrochloric acid at low temperatures affords cis products 7a-e with diastereomeric ratios of up to 98:2.
• Synthesis of 3-Substituted 4-Piperidinones via a One-Pot Tandem Oxidation−Cyclization−Oxidation Process:  Stereodivergent Reduction to 3,4-Disubstituted Piperidines
  作者：Perdip S. Bahia、John S. Snaith

  DOI：10.1021/jo0357418

  日期：2004.4.1

  A novel approach to 3-substituted 4-piperidinones is described. The one-pot tandem oxidation - cyclization - oxidation of unsaturated alcohols 1a-e by PCC or PCC and trifluoromethanesulfonic acid affords piperidinones 2a-e in good yield. Reduction of 2a-e by L-Selectride gives the corresponding cis 3,4-disubstituted piperidines with diastereomeric ratios of >99:1. By contrast, reduction of 2a-e by Al-isopropoxydiisobutylalane gives the trans products with diastereomeric ratios of up to 99:1.