1-phenylseleno-2-(p-toluenesulfonyl)ethyne | 168064-94-6

• 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: 1-phenylseleno-2-(p-toluenesulfonyl)ethyne
• 英文别名: 1-Methyl-4-(2-phenylselanylethynylsulfonyl)benzene
• CAS: 168064-94-6
• 化学式: C₁₅H₁₂O₂SSe
• 分子量: 335.285
• InChiKey: ZJNUJIGIWQYKNS-UHFFFAOYSA-N

物化性质

• 熔点：
  72-75 °C
• 沸点：
  461.4±38.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.72
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-phenylseleno-2-(p-toluenesulfonyl)ethyne 在 sodium tetrahydroborate 、 sodium hydride 、 nickel dichloride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 13.25h， 生成 1-propoxy-1-(p-toluenesulfonyl)ethene
  参考文献：
  名称：

  Additions of Organocopper Reagents and Heteroatom Nucleophiles to 1-Phenylseleno-2-(p-toluenesulfonyl)ethyne. Preparation of Vinyl and Allenic Sulfones and Formation of Michael, Anti-Michael, and Rearrangement Products

  摘要：

  1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (4) was produced nearly quantitatively from p-(toluenesulfonyl)ethyne and benzeneselenenyl chloride. It underwent stereo- and regioselective syn-additions of organocopper reagents RCu(CN)Li to the beta-position of the sulfone moiety to afford adducts 5. Further reaction of the products with reagents RCu(SePh)Li resulted in substitution of the phenylseleno group with retention of configuration. Control of E,Z-stereochemistry in the product beta,beta-disubstituted vinyl sulfones is therefore achieved by the order of addition of the reagents. Selenoxide syn-elimination of adducts 5 afforded the corresponding allenic sulfones. The additions of amines and alkoxides to 4 produced the corresponding anti-Michael regioisomers (where attack occurred a to the sulfone group) as the major or sole products. The additions were highly stereoselective, proceeding by anti-addition in the anti-Michael series and by syn-addition in the corresponding Michael regioisomers. The reactions of 4 with thiolates and selenolates were more complex, affording rearranged adducts and Michael adducts as the major and minor products, respectively. The formation of the rearranged products can be rationalized by a series of addition-elimination processes. Phenylselenoethyne (43) underwent conjugate additions of pyrrolidine, sodium methoxide, sodium ethanethiolate, and benzeneselenolate anion, affording the corresponding cis isomers via anti-addition. The experiments with heteroatom nucleophiles and acetylenes 4 and 43 show that the phenylseleno group has a surprisingly large activating effect upon conjugate additions.

  DOI：

  10.1021/jo981224r
• 作为产物：
  描述：

  苯基氯化硒 、 乙炔基对甲苯基砜 在 三乙胺 作用下， 生成 1-phenylseleno-2-(p-toluenesulfonyl)ethyne
  参考文献：
  名称：

  Additions of Organocopper Reagents and Heteroatom Nucleophiles to 1-Phenylseleno-2-(p-toluenesulfonyl)ethyne. Preparation of Vinyl and Allenic Sulfones and Formation of Michael, Anti-Michael, and Rearrangement Products

  摘要：

  1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (4) was produced nearly quantitatively from p-(toluenesulfonyl)ethyne and benzeneselenenyl chloride. It underwent stereo- and regioselective syn-additions of organocopper reagents RCu(CN)Li to the beta-position of the sulfone moiety to afford adducts 5. Further reaction of the products with reagents RCu(SePh)Li resulted in substitution of the phenylseleno group with retention of configuration. Control of E,Z-stereochemistry in the product beta,beta-disubstituted vinyl sulfones is therefore achieved by the order of addition of the reagents. Selenoxide syn-elimination of adducts 5 afforded the corresponding allenic sulfones. The additions of amines and alkoxides to 4 produced the corresponding anti-Michael regioisomers (where attack occurred a to the sulfone group) as the major or sole products. The additions were highly stereoselective, proceeding by anti-addition in the anti-Michael series and by syn-addition in the corresponding Michael regioisomers. The reactions of 4 with thiolates and selenolates were more complex, affording rearranged adducts and Michael adducts as the major and minor products, respectively. The formation of the rearranged products can be rationalized by a series of addition-elimination processes. Phenylselenoethyne (43) underwent conjugate additions of pyrrolidine, sodium methoxide, sodium ethanethiolate, and benzeneselenolate anion, affording the corresponding cis isomers via anti-addition. The experiments with heteroatom nucleophiles and acetylenes 4 and 43 show that the phenylseleno group has a surprisingly large activating effect upon conjugate additions.

  DOI：

  10.1021/jo981224r

文献信息

• 1-(Phenylseleno)-2-(p-toluenesulfonyl)ethyne. A Novel Acetylenic Sulfone That Undergoes Normal and Anti-Michael Nucleophilic Additions
  作者：T Back

  DOI：10.1016/00404-0399(50)09253-

  日期：1995.7.3
• Cycloaddition Reactions of 1-Phenylseleno-2-(<i>p</i>-toluenesulfonyl)ethyne
  作者：Thomas G. Back、Richard J. Bethell、Masood Parvez、Jerry A. Taylor、Daniel Wehrli

  DOI：10.1021/jo990730t

  日期：1999.10.1

  1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (1) is an effective dienophile and dipolarophile. It underwent facile Diels-Alder reactions with a variety of dienes to afford vicinal sulfone- and selenide-functionalized 1,4-cyclohexadienes. Unexpected regiochemistry that is the opposite of what is obtained with simple acetylenic sulfones was observed with several unsymmetrical dienes containing methyl or methoxy substituents at the 1- or 2-position. Acetylene 1 reacted with (trimethylsilyl)methyl azide, diazomethane, and 2,4,6-trimethylbenzonitrile N-oxide via 1,3-dipolar cycloadditions to afford the corresponding triazole, 1,2-diazole, and isoxazole products. It also underwent an ene reaction with beta-pinene that showed anomalous regiochemistry compared to other acetylenic sulfones. The Diels-Alder cycloadducts obtained from the reaction of 1 with 2,3-dimethyl-1,3,butadiene and 1,3-cyclohexadiene were readily converted into the corresponding beta-keto sulfones and ketones, thus rendering 1 as the synthetic equivalent of p-toluenesulfonylketene and ketene, respectively. Base-catalyzed elimination of TsOH from the Diels-Alder cycloadduct obtained with 2,3-dimethyl-1,3-butadiene afforded the corresponding aryl phenyl selenide, while the adduct from piperylene underwent oxidation to its selenoxide, followed by a Pummerer-type reaction to produce 2-(phenylseleno)-3-(p-toluenesulfonyl)toluene. The reaction of the bicyclic Diels-Alder product obtained from 1,3-cyclohexadiene with MeCu(SePh)Li resulted in substitution of the phenylseleno moiety by a methyl group, whereas similar treatment, of the monocyclic adduct derived from piperylene effected elimination of PhSeH and aromatization.
• Additions of Organocopper Reagents and Heteroatom Nucleophiles to 1-Phenylseleno-2-(<i>p</i>-toluenesulfonyl)ethyne. Preparation of Vinyl and Allenic Sulfones and Formation of Michael, Anti-Michael, and Rearrangement Products
  作者：Thomas G. Back、Richard J. Bethell、Masood Parvez、Daniel Wehrli

  DOI：10.1021/jo981224r

  日期：1998.10.1

  1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (4) was produced nearly quantitatively from p-(toluenesulfonyl)ethyne and benzeneselenenyl chloride. It underwent stereo- and regioselective syn-additions of organocopper reagents RCu(CN)Li to the beta-position of the sulfone moiety to afford adducts 5. Further reaction of the products with reagents RCu(SePh)Li resulted in substitution of the phenylseleno group with retention of configuration. Control of E,Z-stereochemistry in the product beta,beta-disubstituted vinyl sulfones is therefore achieved by the order of addition of the reagents. Selenoxide syn-elimination of adducts 5 afforded the corresponding allenic sulfones. The additions of amines and alkoxides to 4 produced the corresponding anti-Michael regioisomers (where attack occurred a to the sulfone group) as the major or sole products. The additions were highly stereoselective, proceeding by anti-addition in the anti-Michael series and by syn-addition in the corresponding Michael regioisomers. The reactions of 4 with thiolates and selenolates were more complex, affording rearranged adducts and Michael adducts as the major and minor products, respectively. The formation of the rearranged products can be rationalized by a series of addition-elimination processes. Phenylselenoethyne (43) underwent conjugate additions of pyrrolidine, sodium methoxide, sodium ethanethiolate, and benzeneselenolate anion, affording the corresponding cis isomers via anti-addition. The experiments with heteroatom nucleophiles and acetylenes 4 and 43 show that the phenylseleno group has a surprisingly large activating effect upon conjugate additions.