(5S)-4-aza-1-hydroxy-7-oxa-5-phenyl-4-(p-toluenesulfonyl)cycloheptane | 903516-29-0

• 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: (5S)-4-aza-1-hydroxy-7-oxa-5-phenyl-4-(p-toluenesulfonyl)cycloheptane
• 英文别名: (3S)-4-(4-methylphenyl)sulfonyl-3-phenyl-1,4-oxazepan-7-ol
• CAS: 903516-29-0
• 化学式: C₁₈H₂₁NO₄S
• 分子量: 347.435
• InChiKey: NCVVNZAXMLHUFV-QNSVNVJESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  75.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (5S)-4-aza-1-hydroxy-7-oxa-5-phenyl-4-(p-toluenesulfonyl)cycloheptane 、 (叔丁氧基羰基亚甲基)三苯基磷烷 在 苯甲酸 作用下， 以 甲苯 为溶剂， 反应 1.0h， 生成 tert-butyl (2Z,7S)-6-aza-8-hydroxy-7-phenyl-6-(p-toluenesulfonyl)oct-2-enoate 、 tert-butyl (2E,7S)-6-aza-8-hydroxy-7-phenyl-6-(p-toluenesulfonyl)oct-2-enoate
  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：

  (S)-N-(2-hydroxy-1-phenylethyl)-4-methylbenzenesulfonamide 在 咪唑 、 盐酸 、 水 、 caesium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 108.0h， 生成 (5S)-4-aza-1-hydroxy-7-oxa-5-phenyl-4-(p-toluenesulfonyl)cycloheptane
  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

• 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.