tert-butyl-8-(diamino)naphthyl-(-)-menthyltin(IV) bromide | 142189-17-1

• 英文名称: tert-butyl-8-(diamino)naphthyl-(-)-menthyltin(IV) bromide
• CAS: 142189-17-1
• 化学式: C₂₆H₄₀BrNSn
• 分子量: 565.224
• InChiKey: XPZZCZHQFNTNGD-LQFJUXDWSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  tert-butyl-8-(diamino)naphthyl-(-)-menthyltin(IV) bromide 、 lithium aluminium tetrahydride 以 乙醚 为溶剂， 以93%的产率得到tert-butyl-8-(dimethylamino)naphthyl-(-)-menthyltin(IV) hydride
  参考文献：
  名称：

  Synthesis and characterization of chiral (-)-menthyltin(IV) compounds. X-ray structure of tert-butyl-8-(dimethylamino)naphthyl-(-)-menthyltin hydride

  摘要：

  A series of optically active (-)-menthyltin(IV) derivatives with tin directly bound to a chiral carbon atom has been synthesized and characterized. The Grignard reagent derived from (-)-menthyl chloride stereospecifically reacts with trimethyltin chloride to afford (-)-menthyltrimethyltin (1). 1 is derivatized by selective bromodemetalation, alkylation, and hydrogenation, yielding (-)-menthyldimethyltin bromide (2), tert-butyl-(-)-menthyldimethyltin (3), tert-butyl-(-)-menthyltin dibromide (4), and each prochiral at the tin center as well as tert-butyl-8-(dimethylamino)naphthyl-(-)-menthyltin bromide (5) and hydride (6), in which an additional center of asymmetry has been created at the tin atom. By means of multinuclear NMR investigations, the conformation of the optically active ligand in 1-6 was determined, the coordination behavior of the potentially bidentate aminonaphthyl ligand in 5 and 6, resulting in a trigonal bipyramidal (5) or a distorted tetrahedral (6) structure in solution, was established, and for 5 and 6, the ratio of epimers differing in the absolute configuration at the tin center was determined to be 45:55 and 40:60, respectively. The single-crystal X-ray structural analysis of 6 revealed a pair of R(Sn)/S(Sn) epimers. 6 crystallizes monoclinically, space group P2(1), with a = 17.786 (8) angstrom, b = 10.890 (4) angstrom, c = 13.700 (8) angstrom, beta = 108.0 (4)-degrees, and Z = 4. The structure was solved from 4449 observed reflections with I greater-than-or-equal-to 3-sigma(I) and refined to a final R factor of 0.028. The coordination geometry around tin for the two molecules in the asymmetric unit is that of a trigonal bipyramidal-like monocapped tetrahedron showing a very weak Sn-N interaction with a Sn-N distance of 2.931 (3) (molecule A) or 2.885 (3) angstrom (molecule B). The Sn-H bond lengths are 1.52 (5) and 1.63 (5) angstrom, respectively.

  DOI：

  10.1021/om00044a019
• 作为产物：
  描述：

  tert-butyl-(-)-menthyltin(IV) dibromide 、 8-dimethylamino-1-naphthyllithium*(diethyl ether) 以 乙醚 为溶剂， 以60%的产率得到tert-butyl-8-(diamino)naphthyl-(-)-menthyltin(IV) bromide
  参考文献：
  名称：

  Synthesis and characterization of chiral (-)-menthyltin(IV) compounds. X-ray structure of tert-butyl-8-(dimethylamino)naphthyl-(-)-menthyltin hydride

  摘要：

  A series of optically active (-)-menthyltin(IV) derivatives with tin directly bound to a chiral carbon atom has been synthesized and characterized. The Grignard reagent derived from (-)-menthyl chloride stereospecifically reacts with trimethyltin chloride to afford (-)-menthyltrimethyltin (1). 1 is derivatized by selective bromodemetalation, alkylation, and hydrogenation, yielding (-)-menthyldimethyltin bromide (2), tert-butyl-(-)-menthyldimethyltin (3), tert-butyl-(-)-menthyltin dibromide (4), and each prochiral at the tin center as well as tert-butyl-8-(dimethylamino)naphthyl-(-)-menthyltin bromide (5) and hydride (6), in which an additional center of asymmetry has been created at the tin atom. By means of multinuclear NMR investigations, the conformation of the optically active ligand in 1-6 was determined, the coordination behavior of the potentially bidentate aminonaphthyl ligand in 5 and 6, resulting in a trigonal bipyramidal (5) or a distorted tetrahedral (6) structure in solution, was established, and for 5 and 6, the ratio of epimers differing in the absolute configuration at the tin center was determined to be 45:55 and 40:60, respectively. The single-crystal X-ray structural analysis of 6 revealed a pair of R(Sn)/S(Sn) epimers. 6 crystallizes monoclinically, space group P2(1), with a = 17.786 (8) angstrom, b = 10.890 (4) angstrom, c = 13.700 (8) angstrom, beta = 108.0 (4)-degrees, and Z = 4. The structure was solved from 4449 observed reflections with I greater-than-or-equal-to 3-sigma(I) and refined to a final R factor of 0.028. The coordination geometry around tin for the two molecules in the asymmetric unit is that of a trigonal bipyramidal-like monocapped tetrahedron showing a very weak Sn-N interaction with a Sn-N distance of 2.931 (3) (molecule A) or 2.885 (3) angstrom (molecule B). The Sn-H bond lengths are 1.52 (5) and 1.63 (5) angstrom, respectively.

  DOI：

  10.1021/om00044a019