(2E)-methyl 6-aza-8-(tert-butyldimethylsilyloxy)-6-(p-toluenesulfonyl)oct-2-enoate | 903516-18-7

• 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: (2E)-methyl 6-aza-8-(tert-butyldimethylsilyloxy)-6-(p-toluenesulfonyl)oct-2-enoate
• 英文别名: methyl (E)-5-[2-[tert-butyl(dimethyl)silyl]oxyethyl-(4-methylphenyl)sulfonylamino]pent-2-enoate
• CAS: 903516-18-7
• 化学式: C₂₁H₃₅NO₅SSi
• 分子量: 441.664
• InChiKey: VTYSXNDYMGXWRN-CSKARUKUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.13
• 重原子数：
  29
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  81.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2E)-methyl 6-aza-8-(tert-butyldimethylsilyloxy)-6-(p-toluenesulfonyl)oct-2-enoate 在 偶氮二异丁腈 、 三正丁基氢锡 、 二溴三苯基膦 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 20.0h， 生成 1-(p-toluenesulfonyl)-4-(methoxycarbonylmethyl)piperidine
  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：

  N-(2-((tert-butyldimethylsilyl)oxy)ethyl)-4-methylbenzenesulfonamide 在 二异丁基氢化铝 、 potassium carbonate 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 98.0h， 生成 (2E)-methyl 6-aza-8-(tert-butyldimethylsilyloxy)-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

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.