(S)-N-(p-toluenesulfonyl)-isoleucinol | 898558-08-2

• 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)-isoleucinol
• 英文别名: (2S,3S)-N-(4-toluenesulfonyl)-2-amino-3-methyl-pentanol；N-tosylisoleucinol；Phenylsulfonamide, 2g；N-[(2S,3S)-1-hydroxy-3-methylpentan-2-yl]-4-methylbenzenesulfonamide
• CAS: 898558-08-2
• 化学式: C₁₃H₂₁NO₃S
• 分子量: 271.381
• InChiKey: DOTYVOXSVPEJGB-WCQYABFASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  18
• 可旋转键数：
  6
• 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)-isoleucinol 在 咪唑 、 盐酸 、 偶氮二异丁腈 、 水 、 三正丁基氢锡 、 caesium carbonate 、 三乙胺 、 苯甲酸 、 lithium bromide 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 206.0h， 生成 (2R,4S)-2-((S)-sec-butyl)-4-(tert-butoxycarbonylmethyl)-1-(p-toluenesulfonyl)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：

  3-methyl-2-{[(4-methylphenyl)sulfonyl]amino}pentanoic acid 在 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 反应 16.17h， 生成 (S)-N-(p-toluenesulfonyl)-isoleucinol
  参考文献：
  名称：

  对映体纯的二氢-1H-a庚因的合成和杂Diels-Alder反应。

  摘要：

  对映体纯的3-取代的7,7-二卤-2-氮杂双环[4.1.0]庚烷在K 2 CO 3的存在下热解可得到高产率的2-烷基-6-卤代-1-甲苯基-2,3-二氢-1 H-氮杂。它们在Suzuki条件下与异二烯体进行高度立体选择性的[4 + 2]环加成反应，并进行芳基化/烯基化。

  DOI：

  10.1039/d0cc04413j

文献信息

• 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）
• Synthesis of novel N-protected β3-amino nitriles: study of their hydrolysis involving a nitrilase-catalyzed step
  作者：Maité Sylla-Iyarreta Veitía、Pierre Louis Brun、Pierre Jorda、Annie Falguières、Clotilde Ferroud

  DOI：10.1016/j.tetasy.2009.07.045

  日期：2009.9

  Several commercially available nitrilases were investigated with regard to their potential to hydrolyze N-protected beta(3)-amino nitriles into their corresponding N-protected beta(3)-amino acids.The biotransformations were obtained in different proportions depending oil the nitrilase involved The best hydrolysis results were achieved for the N-Cbz-beta(3)-amino nitrile from i-alanine using the NIT-107, in a phosphate buffer at 0 05 M However, no biotransformation into the corresponding acids was observed for the N-sulfonylamide beta(3)-amino nitriles. Two simple and efficient procedures to prepare the beta(3)-amino nitriles from their analogous alpha-amino acids are described Thirty four new substances were synthesized and characterized over the course of this work. (C) 2009 Elsevier Ltd All rights reserved
• Discovery of a novel series of Notch-sparing γ-secretase inhibitors
  作者：Anthony Kreft、Boyd Harrison、Suzan Aschmies、Kevin Atchison、David Casebier、Derek C. Cole、George Diamantidis、John Ellingboe、Diane Hauze、Yun Hu、Donna Huryn、Mei Jin、Dennis Kubrak、Peimin Lu、Joseph Lundquist、Charles Mann、Robert Martone、William Moore、Aram Oganesian、Alex Porte、Dave R. Riddell、June Sonnenberg-Reines、Joseph R. Stock、Shaiu-Ching Sun、Erik Wagner、Kevin Woller、Zheng Xu、Hua Zhou、J. Steven Jacobsen

  DOI：10.1016/j.bmcl.2008.05.064

  日期：2008.7

  Using a cell-based assay, we have identified a new series of Notch-sparing gamma-secretase inhibitors from HTS screening leads 2a and 2e. Lead optimization studies led to the discovery of analog 8e with improved gamma-secretase inhibitory potency and Notch-sparing selectivity. (C) 2008 Elsevier Ltd. All rights reserved.
• 3,3‘-Oxazolidinyl-Substituted 2,2‘-Biphenyldiols:  Novel Tropos Ligands with a Large Induction on the Chiral Axis
  作者：Stefan Wünnemann、Roland Fröhlich、Dieter Hoppe

  DOI：10.1021/ol060528u

  日期：2006.6.1

  A novel type of bisphenol ligand is presented which provides high modularity. Chiral information is introduced in the 3,3 '-positions as N-arenesulfonyl-1,3-oxazolidines inducing an unexpectedly high diastereoselectivity of up to 98: 2 onto the chiral axis. The impact of each part of the molecule on the diastereomeric ratio is evaluated with extended variable-temperature (VT) NMR studies. A first example of application in asymmetric catalysis is given.
• Synthesis and hetero-Diels–Alder reactions of enantiomerically pure dihydro-1<i>H</i>-azepines
  作者：Donald Craig、Samuel R. J. Spreadbury、Andrew J. P. White

  DOI：10.1039/d0cc04413j

  日期：——

  Thermolysis of enantiomerically pure 3-substituted 7,7-dihalo-2-azabicyclo[4.1.0]heptanes in the presence of K2CO3 gives in good yields 2-alkyl-6-halo-1-tosyl-2,3-dihydro-1H-azepines. These undergo highly stereoselective [4+2] cycloaddition reactions with heterodienophiles and arylation/alkenylation under Suzuki conditions.

  对映体纯的3-取代的7,7-二卤-2-氮杂双环[4.1.0]庚烷在K 2 CO 3的存在下热解可得到高产率的2-烷基-6-卤代-1-甲苯基-2,3-二氢-1 H-氮杂。它们在Suzuki条件下与异二烯体进行高度立体选择性的[4 + 2]环加成反应，并进行芳基化/烯基化。