(S)-N-(p-toluenesulfonyl)-tert-butylglycinol | 887255-41-6

• 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)-N-(p-toluenesulfonyl)-tert-butylglycinol
• 英文别名: (2S)-N-(4-toluenesulfonyl)-2-amino-3,3-dimethyl-butanol；N-tosyl-tert-leucinol；(S)-(+)-N-(1-hydroxymethyl-2,2-dimethylpropyl)-4-methylbenzenesulfonamide；N-[(2S)-1-hydroxy-3,3-dimethylbutan-2-yl]-4-methylbenzenesulfonamide
• CAS: 887255-41-6
• 化学式: C₁₃H₂₁NO₃S
• 分子量: 271.381
• InChiKey: PIIPRXDFNOYPBH-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  74.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-N-(p-toluenesulfonyl)-tert-butylglycinol 在 咪唑 、 盐酸 、 水 、 caesium carbonate 、 苯甲酸 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 109.0h， 生成 methyl (2E,7S)-6-aza-7-tert-butyl-8-hydroxy-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)-4-methyl-benzenesulfinic acid (2,2-dimethyl-propylidene)-amide 在 sodium tetrahydroborate 、 1,3-二溴-5,5-二甲基海因 作用下， 以 四氢呋喃 为溶剂， 生成 (S)-N-(p-toluenesulfonyl)-tert-butylglycinol
  参考文献：
  名称：

  从亚磺胺（N-亚磺酰基亚胺）衍生的α-氨基1，3-二硫杂环丁烷不对称合成α-氨基醛。（-）-2,3-反-3,4-顺式-二羟基脯氨酸的形式合成

  摘要：

  用1，3-二溴-5，5-二甲基乙内酰脲水溶液水解亚磺胺衍生的N-亚磺酰基α-氨基1，2-二硫杂环丁烷以良好的收率和高对映体纯度得到相应的N-甲苯磺酰基α-氨基醛。这些醛可以还原为氨基醇，并进行Wittig反应，生成烯丙基胺而没有差向异构化。在（-）-2,3-反式-3,4-顺式-二羟基脯氨酸的正式合成中说明了该方法的实用性。

  DOI：

  10.1016/j.tetlet.2006.02.092

文献信息

• Asymmetric synthesis of N-tosyl amino acids from N-sulfinyl α-amino-1,3-dithioketals
  作者：Franklin A. Davis、Tokala Ramachandar、Jing Chai、Hiu Qiu

  DOI：10.3998/ark.5550190.0011.804

  日期：——

  Hydrolysis of diastereomerically pure N-sulfinyl -amino-1,3-dithianes with 1,3-dibromo-5,5dimethylhydantoin gives N-tosyl -amino aldehydes which when subjected to a Pinnick-type oxidation gave N-tosyl -amino acids without epimerization.

  用 1,3-二溴-5,5 二甲基乙内酰脲水解非对映体纯 N-亚磺酰基 α-氨基-1,3-二噻烷生成 N-甲苯磺酰基 α-氨基醛，当进行 Pinnick 型氧化时生成 N-甲苯磺酰基 α-氨基没有差向异构化的酸。
• Asymmetric Strecker Reaction ofN-Benzhydrylimines Utilising New Tropos Biphenyldiol-Based Ligands
  作者：Stefan Wünnemann、Roland Fröhlich、Dieter Hoppe

  DOI：10.1002/ejoc.200700763

  日期：2008.2

  intermediates together with easily accessible N-arenesulfonylamino alcohols furnish a broad variety of 1,3-oxazolidines. These are applied as chiral tropos ligands in a titanium-mediated Strecker-type reaction of N-benzhydrylimines. A correlation between the ee values in the product and the diastereomeric ratio concerning the chiral axis of the ligand is made. Those substituents in the ligand which proved

  介绍了 N-arenesulfonyl-1,3-oxazolidinyl 取代的联苯二醇库的合成。一组两个中心中间体与易于获得的 N-芳烃磺酰氨基醇一起提供了种类繁多的 1,3-恶唑烷。这些在钛介导的 N-二苯甲基亚胺的 Strecker 型反应中用作手性原配体。在产物中的ee值和关于配体手性轴的非对映体比率之间建立相关性。配体中的那些取代基被证明导致对相关化合物中手性轴的一种非对映异构体的更高偏好，现在提供了最具选择性的配体。在 13 次筛选中的 8 次中发现了两种特权配体，可提供优异的结果。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008）
• Gold-Catalyzed Direct Activation of Allylic Alcohols in the Stereoselective Synthesis of Functionalized 2-Vinyl-Morpholines
  作者：Marco Bandini、Magda Monari、Alessandro Romaniello、Michele Tragni

  DOI：10.1002/chem.201002606

  日期：2010.12.27

  Alcohol versus alcohol: A highly stereocontrolled synthesis of substituted morpholines is realized by means of gold‐catalyzed dehydrative allylic cyclization of diols (see scheme for one example; segphos = 5,5′‐bis[di(3,5‐di‐tert‐butyl‐4‐methyoxyphenyl)phosphine]‐4,4′‐bi‐1,3‐benzodioxole). The present methodology represents one of the few examples of enantioselective gold‐catalyzed transformations

  醇与醇：一个高度立体控制取代的吗啉的合成是通过二醇的金催化的脱水环化烯丙基（参见，一个示例方案来实现的; SEGPHOS = 5,5'-双[二（3,5-二-叔-丁基-4-甲氧基苯基）膦] -4,4'-bi-1,3-苯并二恶唑）。本方法学代表了涉及未活化烯烃的对映选择性金催化转化的少数实例之一。
• Asymmetric synthesis of α-amino aldehydes from sulfinimine (N-sulfinyl imine)-derived α-amino 1,3-dithianes. Formal synthesis of (−)-2,3-trans-3,4-cis-dihydroxyproline
  作者：Franklin A. Davis、Tokala Ramachandar、Jing Chai、Eduardas Skucas

  DOI：10.1016/j.tetlet.2006.02.092

  日期：2006.4

  sulfinimine-derived N-sulfinyl α-amino 1,3-dithianes with aqueous 1,3-dibromo-5,5-dimethylhydantoin affords the corresponding N-tosyl α-amino aldehydes in good yield and high enantiomeric purity. These aldehydes can be reduced to amino alcohols and undergo the Wittig reaction to give allylic amines without epimerization. The utility of this methodology is illustrated in a formal synthesis of (−)-2,3-trans-3,4-cis-dihydroxyproline

  用1，3-二溴-5，5-二甲基乙内酰脲水溶液水解亚磺胺衍生的N-亚磺酰基α-氨基1，2-二硫杂环丁烷以良好的收率和高对映体纯度得到相应的N-甲苯磺酰基α-氨基醛。这些醛可以还原为氨基醇，并进行Wittig反应，生成烯丙基胺而没有差向异构化。在（-）-2,3-反式-3,4-顺式-二羟基脯氨酸的正式合成中说明了该方法的实用性。
• 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.