4,5-dihydro-4-methyl-3H-dinaphtho<2,1-c:1',2'-e>thiepinium perchlorate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并硫平类
• 英文名称: 4,5-dihydro-4-methyl-3H-dinaphtho<2,1-c:1',2'-e>thiepinium perchlorate
• 英文别名: 13-methyl-13-thioniapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene;perchlorate
• 化学式: C₂₃H₁₉S*ClO₄
• 分子量: 426.92
• InChiKey: AAWQUWLQTIFTES-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.17
• 重原子数：
  29
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  75.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,5-dihydro-4-methyl-3H-dinaphtho<2,1-c:1',2'-e>thiepinium perchlorate 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 以96%的产率得到2-(azidomethyl)-2'-<(methylthio)methyl>-1,1'-binaphthyl
  参考文献：
  名称：

  Nucleophilic Attack on 4,5-Dihydro-4-alkyl-3H-dinaphtho[2,1-c:1',2'-e]thiepinium Salts. A Convenient Approach to New 2,2'-Bidentate 1,1'-Binaphthalene Ligands with Sulfur Donor Atoms

  摘要：

  The title dihydrothiepinium salts 6 react with a wide range of N-, S-, Se-, O-, and C-nucleophiles to afford dihydrothiepin 5 and/or the corresponding bidentate ligands 7. The dual course of the reaction can be controlled by a judicious choice of the substrate counterion. In most instances, an iodide counterion aids formation of dihydrothiepins 5, whereas perchlorate, tetraphenyl borate, or tetrafluoroborate counterions favor formation of bidentate ligands 7. An explanation based on a competition between the counterion and the external nucleophile is provided. Dihydrothiepinium salts 6 are easily accessible from dibromide (R,S)-4 via dihydrothiepin (R,S)-5. Individual enantiomers (R)- and (S)-5 have been obtained by resolution on a preparative triacetylcellulose (TAC) column and assigned absolute configuration on the basis of CD spectra and chemical correlation.

  DOI：

  10.1021/jo00085a021
• 作为产物：
  描述：

  4,5-dihydro-4-methyl-3H-dinaphtho<2,1-c:1',2'-e>thiepinium iodide 在 sodium tetrahydroborate 、 silver perchlorate 作用下， 以 硝基甲烷 、 二氯甲烷 为溶剂， 反应 0.17h， 生成 4,5-dihydro-4-methyl-3H-dinaphtho<2,1-c:1',2'-e>thiepinium perchlorate
  参考文献：
  名称：

  Nucleophilic Attack on 4,5-Dihydro-4-alkyl-3H-dinaphtho[2,1-c:1',2'-e]thiepinium Salts. A Convenient Approach to New 2,2'-Bidentate 1,1'-Binaphthalene Ligands with Sulfur Donor Atoms

  摘要：

  The title dihydrothiepinium salts 6 react with a wide range of N-, S-, Se-, O-, and C-nucleophiles to afford dihydrothiepin 5 and/or the corresponding bidentate ligands 7. The dual course of the reaction can be controlled by a judicious choice of the substrate counterion. In most instances, an iodide counterion aids formation of dihydrothiepins 5, whereas perchlorate, tetraphenyl borate, or tetrafluoroborate counterions favor formation of bidentate ligands 7. An explanation based on a competition between the counterion and the external nucleophile is provided. Dihydrothiepinium salts 6 are easily accessible from dibromide (R,S)-4 via dihydrothiepin (R,S)-5. Individual enantiomers (R)- and (S)-5 have been obtained by resolution on a preparative triacetylcellulose (TAC) column and assigned absolute configuration on the basis of CD spectra and chemical correlation.

  DOI：

  10.1021/jo00085a021

文献信息

• Stereochemical Dichotomy in the Stevens Rearrangement of Axially Twisted Dihydroazepinium and Dihydrothiepinium Salts. A Novel Enantioselective Synthesis of Pentahelicene
  作者：Irena G. Stara、Ivo Stary、Milos Tichy、Jiri Zavada、Vladimir Hanus

  DOI：10.1021/ja00091a009

  日期：1994.6

  Evidence is presented indicating that the stereochemistry of the Stevens rearrangement of the axially chiral onium salts 1a-d and 5 is dramatically structure-dependent. Thus, the binaphthyl ammonium salts (S)-(+)-1a-c react with a strong base with exclusive (100% de) formation of the corresponding rearranged amines (R,3R)-(+)-2a-c, demonstrating a complete transfer of the (S) axial dissymmetry/asymmetry into (R) asymmetry of the newly formed carbon center. Exactly opposite stereochemistry was established in an earlier study by Mislow of the biphenyl analogue (S)-(+)-5, yielding the rearranged products (S,9S)-(+)-6 and (R,9S)-(-)-7 with exclusive (S) configuration at the carbon center. Rearrangement of the sulfonium salt 1d is found to be intermediate between the two extremes, yielding a mixture of diastereoisomeric products 2d and 3d, which differ in configuration at the asymmetric carbon center. A direct proof is thus provided that two stereochemically different pathways can participate in the Stevens rearrangement. An explanation is suggested in terms of competition between suprafacial (concerted) and antarafacial (nonconcerted) mechanism.
• Nucleophilic Attack on 4,5-Dihydro-4-alkyl-3H-dinaphtho[2,1-c:1',2'-e]thiepinium Salts. A Convenient Approach to New 2,2'-Bidentate 1,1'-Binaphthalene Ligands with Sulfur Donor Atoms
  作者：Irena G. Stara、Ivo Stary、Milos Tichy、Jiri Zavada、Pavel Fiedler

  DOI：10.1021/jo00085a021

  日期：1994.3

  The title dihydrothiepinium salts 6 react with a wide range of N-, S-, Se-, O-, and C-nucleophiles to afford dihydrothiepin 5 and/or the corresponding bidentate ligands 7. The dual course of the reaction can be controlled by a judicious choice of the substrate counterion. In most instances, an iodide counterion aids formation of dihydrothiepins 5, whereas perchlorate, tetraphenyl borate, or tetrafluoroborate counterions favor formation of bidentate ligands 7. An explanation based on a competition between the counterion and the external nucleophile is provided. Dihydrothiepinium salts 6 are easily accessible from dibromide (R,S)-4 via dihydrothiepin (R,S)-5. Individual enantiomers (R)- and (S)-5 have been obtained by resolution on a preparative triacetylcellulose (TAC) column and assigned absolute configuration on the basis of CD spectra and chemical correlation.