(S)-O-(tert-butyldimethylsilyl)-N-(p-toluenesulfonyl)-valinol | 316363-67-4

• 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)-valinol
• 英文别名: (S)-O-(tert-butyldimethylsilyl)-N-(4-methylbenzenesulfonyl)-valinol；N-[(2S)-1-[tert-butyl(dimethyl)silyl]oxy-3-methylbutan-2-yl]-4-methylbenzenesulfonamide
• CAS: 316363-67-4
• 化学式: C₁₈H₃₃NO₃SSi
• 分子量: 371.616
• InChiKey: BZEZTWPBOZXSRM-QGZVFWFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.32
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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)-valinol 在 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 132.0h， 生成 (5S)-4-aza-1-hydroxy-5-isopropyl-7-oxa-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
• 作为产物：
  描述：

  对甲苯磺酰氯 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)-O-(tert-butyldimethylsilyl)-N-(p-toluenesulfonyl)-valinol
  参考文献：
  名称：

  Selective 7-endo-Cyclization of 3-Aza-5-alkenols through Oxidative Pd(II)-Catalyzed Olefin Oxyarylation

  摘要：

  3-Aza-5-烯醇在与催化Pd(II)物种、CuCl2和ArSnBu3处理时，发生选择性的7-内三端环化反应，生成7-芳基取代的噁唑烷。只有在芳基化步骤存在时，才会发生分子内烷氧化反应，形成一个七元环。否则，会观察到6-外三端反应，生成吗啡啶衍生物。

  DOI：

  10.1055/s-0036-1590939

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.
• Selective 7-endo-Cyclization of 3-Aza-5-alkenols through Oxidative Pd(II)-Catalyzed Olefin Oxyarylation
  作者：Gianluigi Broggini、Silvia Gazzola、Egle Beccalli、Tea Borelli、Carlo Castellano、Daria Diamante

  DOI：10.1055/s-0036-1590939

  日期：2018.3

  3-Aza-5-alkenols undergo selective 7-endo-trig cyclization when treated with a catalytic Pd(II) species, CuCl2 and ArSnBu3 giving 7-aryl-substituted oxazepanes. The intramolecular alkoxylation occurs with formation of a seven-membered ring only when associated with an arylating step. Otherwise, 6-exo-trig reactions, providing morpholine derivatives, were observed.

  3-Aza-5-烯醇在与催化Pd(II)物种、CuCl2和ArSnBu3处理时，发生选择性的7-内三端环化反应，生成7-芳基取代的噁唑烷。只有在芳基化步骤存在时，才会发生分子内烷氧化反应，形成一个七元环。否则，会观察到6-外三端反应，生成吗啡啶衍生物。