(S)-O-(tert-butyldimethylsilyl)-N-(p-toluenesulfonyl)-alaninol | 903516-09-6

• 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)-O-(tert-butyldimethylsilyl)-N-(p-toluenesulfonyl)-alaninol
• 英文别名: N-[(2S)-1-[tert-butyl(dimethyl)silyl]oxypropan-2-yl]-4-methylbenzenesulfonamide
• CAS: 903516-09-6
• 化学式: C₁₆H₂₉NO₃SSi
• 分子量: 343.563
• InChiKey: DYNLGAQFHYUHIC-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  63.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-O-(tert-butyldimethylsilyl)-N-(p-toluenesulfonyl)-alaninol 在 盐酸 、 18-冠醚-6 、 水 、 O,O'-双(2,2,2-三氟乙基)磷乙酸甲酯 、 potassium carbonate 、 caesium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 84.0h， 生成 (S)-2-(toluene-4-sulfonamido)propan-1-ol
  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
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 (S)-2-(toluene-4-sulfonamido)propan-1-ol 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以96%的产率得到(S)-O-(tert-butyldimethylsilyl)-N-(p-toluenesulfonyl)-alaninol
  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.
• Synthesis of 2,4-Disubstituted Piperidines via Radical Cyclization:  Unexpected Enhancement in Diastereoselectivity with Tris(trimethylsilyl)silane
  作者：Lucile A. Gandon、Alexander G. Russell、Tatyana Güveli、Angela E. Brodwolf、Benson M. Kariuki、Neil Spencer、John S. Snaith

  DOI：10.1021/jo060495w

  日期：2006.7.1

  [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.