[(2S,3R)-3-tert-butyl-1-[(1S)-1-(4-methoxyphenyl)ethyl]-2H-1,3-benzazaphosphol-2-yl]-trimethylsilane | 1542704-39-1

• 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: [(2S,3R)-3-tert-butyl-1-[(1S)-1-(4-methoxyphenyl)ethyl]-2H-1,3-benzazaphosphol-2-yl]-trimethylsilane
• CAS: 1542704-39-1
• 化学式: C₂₃H₃₄NOPSi
• 分子量: 399.588
• InChiKey: FXQUCWHZUDOFLQ-ZYYUNJBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.39
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [(2S,3R)-3-tert-butyl-1-[(1S)-1-(4-methoxyphenyl)ethyl]-2H-1,3-benzazaphosphol-2-yl]-trimethylsilane 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 以 四氢呋喃 为溶剂， 反应 48.0h， 以79 mg的产率得到{η¹P-3-tert-butyl-1-[(1S)-1-(p-methoxyphenyl)ethyl]-2-(trimethylsilyl)-2,3-dihydro-1H-1,3-benzazaphosphole}(1,5-octadiene)rhodium chloride
  参考文献：
  名称：

  Enantiomerically Pure N Chirally Substituted 1,3-Benzazaphospholes: Synthesis, Reactivity toward tBuLi, and Conversion to Functionalized Benzazaphospholes and Catalytically Useful Dihydrobenzazaphospholes

  摘要：

  Catalytic C-P coupling of chiral o-bromoanilines 1a-c to the corresponding o-phosphonoanilines 2a-c, reduction to the phosphines 3a-c, and final acid-catalyzed cyclocondensation represents a convenient access to the title compounds 4-c. Reaction of 4a,b with tBuLi allows solvent-dependent directed lithiation leading either to 2-lithiobenzazaphospholes with a P=CLi NR substructure (in Et2O/KOtBu), in the case of anisyl substitution accompanied by partial additional lithiation in o-position of the MeO-group, or to regiospecific "normal" addition with formation of -P-(tBu)-CHLi-NR- species. These were trapped by ClSiMe3, CO2, or MeOH to give the corresponding substitution products 7b, 8b, 10b, 11a,b and 12a,b, respectively. 12a,b, containing the P-C-COOH structural unit, forms with Ni(COD)(2) in THF very efficient ethylene oligomerization catalysts With high selectivity for linear alpha-olefins. The structure elucidation of the products is based on conclusive solution NMR data and crystal structure analyses of the 1-(1S)-anisylethyl compounds 3b and 4b.

  DOI：

  10.1021/om401184n
• 作为产物：
  描述：

  2-[(S)-(1-(p-methoxyphenyl)ethyl)amino]benzenephosphonic acid diethyl ester 在 lithium aluminium tetrahydride 、 三甲基氯硅烷 、 叔丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 96.0h， 生成 [(2S,3R)-3-tert-butyl-1-[(1S)-1-(4-methoxyphenyl)ethyl]-2H-1,3-benzazaphosphol-2-yl]-trimethylsilane 、 3-tert-butyl-1-[(1S)-1-(p-methoxyphenyl)ethyl]-2-(trimethylsilyl)-2,3-dihydro-1H-1,3-benzazaphosphole
  参考文献：
  名称：

  Enantiomerically Pure N Chirally Substituted 1,3-Benzazaphospholes: Synthesis, Reactivity toward tBuLi, and Conversion to Functionalized Benzazaphospholes and Catalytically Useful Dihydrobenzazaphospholes

  摘要：

  Catalytic C-P coupling of chiral o-bromoanilines 1a-c to the corresponding o-phosphonoanilines 2a-c, reduction to the phosphines 3a-c, and final acid-catalyzed cyclocondensation represents a convenient access to the title compounds 4-c. Reaction of 4a,b with tBuLi allows solvent-dependent directed lithiation leading either to 2-lithiobenzazaphospholes with a P=CLi NR substructure (in Et2O/KOtBu), in the case of anisyl substitution accompanied by partial additional lithiation in o-position of the MeO-group, or to regiospecific "normal" addition with formation of -P-(tBu)-CHLi-NR- species. These were trapped by ClSiMe3, CO2, or MeOH to give the corresponding substitution products 7b, 8b, 10b, 11a,b and 12a,b, respectively. 12a,b, containing the P-C-COOH structural unit, forms with Ni(COD)(2) in THF very efficient ethylene oligomerization catalysts With high selectivity for linear alpha-olefins. The structure elucidation of the products is based on conclusive solution NMR data and crystal structure analyses of the 1-(1S)-anisylethyl compounds 3b and 4b.

  DOI：

  10.1021/om401184n