(S)-N-[1-benzyl-2-(tert-butyldimethylsilyloxy)ethyl]-p-toluenesulfonamide | 143260-53-1

• 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: (S)-N-[1-benzyl-2-(tert-butyldimethylsilyloxy)ethyl]-p-toluenesulfonamide
• 英文别名: (S)-O-(tert-butyldimethylsilyl)-N-(p-toluenesulfonyl)-phenylalaninol
• CAS: 143260-53-1
• 化学式: C₂₂H₃₃NO₃SSi
• 分子量: 419.66
• InChiKey: DDZOMFSNGVKPSB-FQEVSTJZSA-N

物化性质

• 沸点：
  508.1±60.0 °C(Predicted)
• 密度：
  1.071±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.91
• 重原子数：
  28.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  55.4
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (S)-N-[1-benzyl-2-(tert-butyldimethylsilyloxy)ethyl]-p-toluenesulfonamide 在 sodium hexamethyldisilazane 、 sodium naphthalenide 作用下， 以 四氢呋喃 、 乙二醇二甲醚 为溶剂， 反应 3.08h， 生成 (S)-N-[1-benzyl-2-(tert-butyldimethylsilyloxy)ethyl]hexadecanamide
  参考文献：
  名称：

  Model Studies toward Scyphostatin: Synthesis of (S)-4-Benzyl-3-(p-toluenesulfonyl)-2-oxazolidinone and Its Effective Transformation to (S)-N-(1-Benzyl-2-hydroxyethyl)hexadecanamide

  摘要：

  DOI：

  10.3987/com-01-s(k)55
• 作为产物：
  描述：

  L-苯丙氨醇 在 咪唑 、 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (S)-N-[1-benzyl-2-(tert-butyldimethylsilyloxy)ethyl]-p-toluenesulfonamide
  参考文献：
  名称：

  Synthesis of 2,4-Disubstituted Piperidines via Radical Cyclization:  Unexpected Enhancement in Diastereoselectivity with Tris(trimethylsilyl)silane

  摘要：

  [GRAPHICS]A novel approach to 2,4-disubstituted piperidines is reported, involving the radical cyclization of 7-substituted-6-aza-8-bromooct-2-enoates. Cyclization with tributyltin hydride affords the trans piperidines with trans/cis diastereomeric ratios ranging typically from 3:1 to 6:1. Cyclization with tris( trimethylsilyl)silane affords the same products with diastereomeric ratios of up to 99: 1 in certain cases. The enhancement in diastereoselectivity results from the selective rearrangement of the minor stereoisomer through a cascade process involving radical cyclization to the piperidine radical, 1,5-radical translocation, and attack of the translocated radical onto the sulfonamide with extrusion of SO2 in a Smiles-type rearrangement. Slower trapping of the piperidine radical by tris(trimethylsilyl) silane compared to tributyltin hydride accounts for the occurrence of the rearrangement cascade in the former case.

  DOI：

  10.1021/jo060495w

文献信息

• Bi(OTf)3 as a Dual Role Catalyst. Synthesis of Substituted Morpholine Derivatives via Catalytic O-Allylation
  作者：Gregory R. Cook、Ryuji Hayashi、Jin-A Park

  DOI：10.3987/com-13-s(s)116

  日期：——

  The diastereoselective synthesis of cis-1,4-disubstituted morpholines has been accomplished in good to excellent yields via Bi(OTf)(3) catalyzed ring-closing O-allylation under mild conditions without the need for added base. The bismuth Lewis acid catalyst appeared to play two roles; the mild deprotection of a silyl ether and the Lewis acid activation of an allylic halide for mild nucelophilic cyclization. Substituted morpholines were obtained with diastereoselectivity ranging from 2:1 to >99:1.