(Z)-5,6-dimethyl-2-phenylseleno-1-(p-toluenesulfonyl)-1,5-heptadiene | 216320-16-0

• 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: (Z)-5,6-dimethyl-2-phenylseleno-1-(p-toluenesulfonyl)-1,5-heptadiene
• 英文别名: 1-[(1Z)-5,6-dimethyl-2-phenylselanylhepta-1,5-dienyl]sulfonyl-4-methylbenzene
• CAS: 216320-16-0
• 化学式: C₂₂H₂₆O₂SSe
• 分子量: 433.473
• InChiKey: IUBNCDPESHISMO-JWGURIENSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.78
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  乙烯基甲醚 、 (Z)-5,6-dimethyl-2-phenylseleno-1-(p-toluenesulfonyl)-1,5-heptadiene 在 copper(l) iodide 、 二甲基硫 、 叔丁基锂 作用下， 生成 6,7-Dimethyl-3-[1-(toluene-4-sulfonyl)-meth-(Z)-ylidene]-oct-6-en-2-one
  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：

  5-溴-2,3-二甲基-2-戊烯 在 三甲基氯硅烷 、 1,1-二溴乙烷 、 sodium iodide 、 lithium chloride 、 锌 作用下， 以 丙酮 为溶剂， 反应 12.0h， 生成 (Z)-5,6-dimethyl-2-phenylseleno-1-(p-toluenesulfonyl)-1,5-heptadiene
  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

• 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.