N-p-Toluolsulfonyl-4,5-dehydro-DL-pipecolinsaeure-methylester, 1-p-Toluolsulfonyl-1,2,3,6-tetrahydro-pyridin-carbonsaeure-(2)-methylester | 92906-71-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-p-Toluolsulfonyl-4,5-dehydro-DL-pipecolinsaeure-methylester, 1-p-Toluolsulfonyl-1,2,3,6-tetrahydro-pyridin-carbonsaeure-(2)-methylester
• 英文别名: 1-(toluene-4-sulfonyl)-1,2,3,6-tetrahydro-pyridine-2-carboxylic acid methyl ester；N-Tosyl-dl-baikiain methyl ester；methyl 1-(4-methylphenyl)sulfonyl-3,6-dihydro-2H-pyridine-2-carboxylate
• CAS: 92906-71-3
• 化学式: C₁₄H₁₇NO₄S
• 分子量: 295.359
• InChiKey: OLKHPCDVNWNHFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-p-Toluolsulfonyl-4,5-dehydro-DL-pipecolinsaeure-methylester, 1-p-Toluolsulfonyl-1,2,3,6-tetrahydro-pyridin-carbonsaeure-(2)-methylester 在 Grubbs catalyst first generation sodium periodate 、 ytterbium(III) chloride 作用下， 以 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 0.33h， 生成 4,5-dihydroxy-1-(toluene-4-sulfonyl)piperidine-2-carboxylic acid methyl ester 、 4,5-dihydroxy-1-(toluene-4-sulfonyl)piperidine-2-carboxylic acid methyl ester
  参考文献：
  名称：

  顺序催化：复分解/二羟基化序列。

  摘要：

  DOI：

  10.1002/anie.200503552
• 作为产物：
  描述：

  2-[Allyl-(toluene-4-sulfonyl)-amino]-pent-4-enoic acid methyl ester 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 14.0h， 生成 N-p-Toluolsulfonyl-4,5-dehydro-DL-pipecolinsaeure-methylester, 1-p-Toluolsulfonyl-1,2,3,6-tetrahydro-pyridin-carbonsaeure-(2)-methylester
  参考文献：
  名称：

  使用基于钌的烯烃复分解催化剂的周转数（TON）研究的意外结果

  摘要：

  对于稀溶液中的闭环复分解（RCM），已经进行了钌基复分解催化剂的周转数（TON）研究。出乎意料的结果表明，1种第一代复分解催化剂可以在比其第二代同行简单未取代的末端烯烃的RCM给予较高TON。特别地，1第一代格拉布催化剂表现出意想不到的高活性，特别是当相对于2种代催化剂。

  DOI：

  10.1002/adsc.200505053

文献信息

• A Novel Polymer-Supported Arene-Ruthenium Complex for Ring-Closing Olefin Metathesis
  作者：Ryo Akiyama、Shū Kobayashi

  DOI：10.1002/1521-3773(20020715)41:14<2602::aid-anie2602>3.0.co;2-3

  日期：2002.7.15
• Novel Ruthenium-Based Metathesis Catalysts Containing Electron- Withdrawing Ligands:  Synthesis, Immobilization, and Reactivity
  作者：Tobias S. Halbach、Stefan Mix、Dirk Fischer、Simon Maechling、Jens O. Krause、Carsten Sievers、Siegfried Blechert、Oskar Nuyken、Michael R. Buchmeiser

  DOI：10.1021/jo0477594

  日期：2005.6.1

  The syntheses and reactivity of seven different ruthenium-based metathesis catalysts are described. Ru(CF3COO)(2)(PCY3)(=CH-2-(2-PrO)C6H4) (1), Ru(CF3COO)(2)(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (2), and Ru(CF3COO)2(PCY3)(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-C6H5) (3) were prepared via chlorine exchange by reacting RuCl2(PCy3)(2)(=CH-2-(2-PrO)C6H4), RuCl2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4), and RuCl2(PCy3)(1,3-dimesityldihydroimidazolin-2-ylidene)(=CHC6H5), respectively, with silver trifluoroacetate (Cy = cyclohexyl). In analogy, Ru(CF3CF2COO)(2)(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (4) and Ru(CF3CF2CF2COO)1(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (5) were prepared from RuCl2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) via reaction with CF3CF2COOAg and CF3CF2CF2COOAg, respectively. Ru(C6F5COO)2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (6) and Ru(C6H4)2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (7) were prepared from RuCl2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) via reaction with C6F5COOTI and C6F5OTI, respectively. Supported catalysts Ru(PS-DVB-CH(2)OOCCF(2)CF(2)CF2COO)(CF2COO)(PCy3)(1,3-dimesityldihydroimidazolin-2-ylidene)(=CHC6H5) (8), Ru(PS-DVBCH2OOCCF2CF2CF2COO)(CF3COO)(PCY3)(=CH-2-(2-PrO)C6H4) (9), and Ru(PS-DVB-CH2OOCCF2CF2CF2COO)(CF3COO)(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4) (10) were synthesized by reaction of RuCl2(PCY3)(1,3-dimesityldihydroimidazolin-2-ylidene)( CHC6H5), RuCl(2)WYA CH-2-(2-PrO)C6H4), and RuCl2(1,3-dimesityldihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4), respectively, with a perfluoroglutaric acid-derivatized poly(styrene-co-divinylbenzene) (PS-DVB) support (silver form). Halogen exchange in PCy3-containing systems had to be carried out in dichloromethane in order to suppress precipitation of AgCl center dot PCy3. The reactivity of all new catalysts in ring-closing metathesis (RCM) of hindered electron-rich and -poor substrates, respectively, at elevated temperature (45 degrees C) was compared with that of existing systems. Diethyl diallylinalonate (DEDAM, 11), diethyl allyl(2-methylallyl)malonate (12), NN-diallyl-p-toluenesulfonamide (13), N-benzyl-N-but-l-en-4-ylbut2-enecarboxylic amide (14), and N-allyl-N-(l-carboxymethyl)but-3-en-1-yl-p-toluenesulfonamide (15) were used as educts. Supported catalysts were prepared with high loadings (2.4, 22.1, and 160 mg of catalyst/g PS-DVB for 8, 9, and 10, respectively). Catalyst 8 showed higher and catalysts 9 and 10 sowed significantly reduced activities in RCM compared to their homogeneous analogues. Thus, with 8, turnover numbers (TONs) up to 4200 were realized in stirred-batch (carousel) RCM experiments.To eucidate the nature of the bound species, catalysts 8-10 were subjected to C-13- and P-31-MAS NMR spectroscopy. These investigations provided evidence for the proposed structures. Leaching of ruthenium into the reaction mixture was low, resulting in ruthenium contents < 85 ppb (ng/g) in the final RCM-derived products.
• US7348290B2
  申请人：——

  公开号：US7348290B2

  公开（公告）日：2008-03-25
• Sequential Catalysis: A Metathesis/Dihydroxylation Sequence
  作者：Samuel Beligny、Stefan Eibauer、Simon Maechling、Siegfried Blechert

  DOI：10.1002/anie.200503552

  日期：2006.3.13
• Unexpected Results of a Turnover Number (TON) Study Utilising Ruthenium-Based Olefin Metathesis Catalysts
  作者：Simon Maechling、Mirko Zaja、Siegfried Blechert

  DOI：10.1002/adsc.200505053

  日期：2005.8

  turnover number (TON) study of ruthenium-based metathesis catalysts has been conducted for ring-closing metathesis (RCM) in dilute solution. Unexpectedly the results indicate that 1st generation metathesis catalysts can give higher TON in RCM of simple unsubstituted terminal olefins than their second generation counterparts. In particular, the 1st generation Hoveyda–Grubbs catalyst showed unexpectedly high

  对于稀溶液中的闭环复分解（RCM），已经进行了钌基复分解催化剂的周转数（TON）研究。出乎意料的结果表明，1种第一代复分解催化剂可以在比其第二代同行简单未取代的末端烯烃的RCM给予较高TON。特别地，1第一代格拉布催化剂表现出意想不到的高活性，特别是当相对于2种代催化剂。