N-[(2S)-2-吡咯烷甲基]-三氟甲磺酰胺 | 782495-18-5

• 物质功能分类: 有机原料 - 杂环化合物
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 中文名称: N-[(2S)-2-吡咯烷甲基]-三氟甲磺酰胺
• 中文别名: N-[(2s)-2-吡咯烷甲基]-三氟甲烷磺酰胺
• 英文名称: (S)-2-(trifluoromethane-sulfonylamino-methyl)-pyrrolidine
• 英文别名: (S)-1,1,1-trifluoro-N-(pyrrolidin-2-ylmethyl)methanesulfonamide；1,1,1-trifluoro-N-[[(2S)-pyrrolidin-2-yl]methyl]methanesulfonamide
• CAS: 782495-18-5
• 化学式: C₆H₁₁F₃N₂O₂S
• 分子量: 232.227
• InChiKey: RIWFUAUXWIEOTK-YFKPBYRVSA-N

物化性质

• 沸点：
  249.6±50.0 °C(Predicted)
• 密度：
  1.377±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  66.6
• 氢给体数：
  2
• 氢受体数：
  7

安全信息

• 危险品标志：
  C
• 安全说明：
  S26,S36/37/39,S45
• 危险类别码：
  R34
• 海关编码：
  2935009090
• WGK Germany：
  3
• 危险品运输编号：
  UN 3263 8/PG 3
• 包装等级：
  III
• 危险类别：
  8
• 危险性防范说明：
  P260,P264,P280,P301+P330+P331,P303+P361+P353,P304+P340,P305+P351+P338,P310,P321,P363,P405,P501
• 危险性描述：
  H314

反应信息

• 作为反应物：
  描述：

  N-[(2S)-2-吡咯烷甲基]-三氟甲磺酰胺 在 sodium hydroxide 作用下， 生成 (S)-2-(氨甲基)吡咯烷
  参考文献：
  名称：

  d-Prolyl-2-（三氟甲基磺酰胺基丙基）吡咯烷：常温条件下醛向β-硝基烯烃的不对称迈克尔加成反应的有机催化剂

  摘要：

  制备了四个2-（三氟甲基磺酰胺基烷基）吡咯烷及其d-脯氨酰胺，并筛选出在室温下且不使用添加剂的情况下，醛与β-硝基烯烃的迈克尔加成反应的有机催化剂。发现d -Prolyl-2-（三氟甲基磺酰胺基丙基）吡咯烷是所研究分子中最好的，它以非常高的产率（高达95％），高的非对映选择性（高达> 99：1）和高的非对映选择性产生γ-硝基醛。具有高达97％的ee。

  DOI：

  10.1021/acs.joc.8b02945
• 作为产物：
  描述：

  (S)-2-氨甲基-1-M-Cbz-吡咯烷 在 palladium on activated charcoal TEA 、 氢气 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 9.5h， 生成 N-[(2S)-2-吡咯烷甲基]-三氟甲磺酰胺
  参考文献：
  名称：

  吡咯烷磺酰胺催化的未改性醛和酮与硝基烯烃的对映和非对映选择性迈克尔加成反应。

  摘要：

  已显示手性（S）-吡咯烷三氟甲磺酰胺可作为醛和酮与硝基烯烃的直接迈克尔加成反应的有效催化剂。作为迈克尔供体的多种醛和酮以及作为受体的硝基烯烃参与了该过程，该过程以高水平的对映选择性（高达99％ee）和非对映选择性（高达50：1 dr）进行。该方法已成功地用于有效的H（3）激动剂Sch 50917的有效合成中。此外，已经开发了一种用于制备（S）-吡咯烷三氟甲烷磺酰胺的实用三步程序。已经通过使用从头算和密度泛函方法研究了由该吡咯烷磺酰胺催化的参与迈克尔加成反应的高水平立体化学控制。已计算出了限速C-C键形成步骤的过渡态结构，该结构对应于关键烯胺中间体的反应构象的表面和表面加成。对这些结构的分析表明，氢键在催化中起重要作用，并且醛在形成2R，3S产物的反应中si-face攻击的能垒比导致2S，3R产物的表面攻击要低。 。相反，在酮的反应中，用于表面添加的能垒比用于硅表面添加的能垒低。在这些迈克尔

  DOI：

  10.1002/chem.200600115
• 作为试剂：
  描述：

  2-环己烯-1-酮 、 N-(苯硒基)邻苯二甲酰亚胺 在 N-[(2S)-2-吡咯烷甲基]-三氟甲磺酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 25.0h， 以63%的产率得到6-(phenylselanyl)cyclohex-2-en-1-one
  参考文献：
  名称：

  Direct, Facile Aldehyde and Ketone α-Selenenylation Reactions Promoted by l-Prolinamide and Pyrrolidine Sulfonamide Organocatalysts

  摘要：

  A new catalytic method for direct alpha-selenenylation reactions of aldehydes and ketones has been developed. The results of exploratory studies have demonstrated that L-prolinamide is an effective catalyst for a-selenenylation reactions of aldehydes, whereas pyrrolidine trifluoromethanesulfonamide efficiently promotes reactions of ketones. Under optimized reaction conditions, using N-(phenylseleno)phthalimide as the selenenylation reagent in CH2Cl2 in the presence of L-prolinamide (2 mol %) or pyrrolidine trifluoromethanesulfonamide (10 mol %), a variety of aldehydes and ketones undergo this process to generate a-selenenylation products in high yields. Mechanistic insight into the L-proline and L-prolinamide catalyzed alpha-selenenylation reactions of aldehydes with N-(phenylseleno)phthalimide has come from theoretical studies employing ab initio methods and density functional theory. The results reveal that (1) the rate-limiting step of the process involves attack of the enamine intermediate at selenium in N-(phenylseleno)phthalimide and (2) the energy of the transition state for the reaction catalyzed by prolinamide is lower than that promoted by proline. This result is consistent with experimental observations. The role of hydrogen bond interactions in stabilizing the transition states for this process is also discussed.

  DOI：

  10.1021/jo0506940

文献信息

• [EN] ORGANOCATALYSTS AND METHODS OF USE IN CHEMICAL SYNTHESIS<br/>[FR] ORGANOCATALYSEURS ET PROCEDES D'UTILISATION DE CES DERNIERS DANS LA SYNTHESE CHIMIQUE
  申请人：STC UNM

  公开号：WO2006007586A1

  公开（公告）日：2006-01-19

  The present invention pertains generally to compositions comprising organocatalysts that facilitate stereo-selective reactions and the method of their synthesis and use. Particularly, the invention relates to metal-free organocatalysts for facilitation of stereo-­selective reactions, and the method of their synthesis and use. These compounds have the structure of the Formulas (I) and (II). Where X is independently selected from CH2, N-Ra, O, S or C=O; Y is CH2, N-Ra, O, S or C=O, with the proviso that at least one of X or Y is CH2, and preferably both of X and Y are CH2; Ra is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 alkyl including a C3-C6 cyclic alkyl group, or an optionally substituted aryl group, preferably an optionally substituted phenyl group; Rb is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 acyclic or a a C3-C6 cyclic alkyl group, CHO, N(Me)O, CO(S)Ra or the group of Formula (III). Where Rc and Rd are each independently H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C12 alkyl, more preferably a C1-C6 alkyl, and an optionally substituted aryl group, or together Rc and Rd form an optionally substituted carbocyclic or optionally substituted heterocyclic ring; R1 is OH, OR, NR'R', NHC(=O)R, NHSO2R; R2 is H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1­C6 alkyl, an optionally substituted aryl group or a =O group (which establishes a carbonyl group with the carbon to which =O is attached; R3 is H, OH, F, C1, Br, I, Cl, an optionally substituted C1-C20 alkyl, alkenyl or alkynyl ('hydrocarbyl') group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl, such that the carbon to which R3 is attached has an R or S configuration; R is H, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group, R' and R' are each independently H, an optionally substituted C1-C20 alkyl group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group; or together R' and R' form an optionally substituted heterocyclic, preferably a 4 to 7 membered optionally substituted heterocyclic group or an optionally substituted heteroaryl ring with the nitrogen to which R' and R' are attached; and wherein said compound is free from a metal catalyst.

  本发明涉及一般包括有机催化剂的组合物，该催化剂促进立体选择性反应以及其合成和使用方法。特别地，本发明涉及无金属有机催化剂以促进立体选择性反应，以及其合成和使用方法。这些化合物具有以下结构的式（I）和（II）。其中X独立地选择自CH2、N-Ra、O、S或C=O；Y为 、N-Ra、O、S或C=O，但至少X或Y中的一个为 ，最好是X和Y都为 ；Ra为H、可选择地取代的C1-C12烷基，最好是可选择地取代的C1-C6烷基，包括C3-C6环烷基，或可选择地取代的芳基，最好是可选择地取代的苯基；Rb为H、可选择地取代的C1-C12烷基，最好是可选择地取代的C1-C6无环或C3-C6环烷基，CHO、N(Me)O、CO(S)Ra或式（III）的基团。其中Rc和Rd各自独立地为H、F、C1、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C12烷基，更好地是C1-C6烷基，以及可选择地取代的芳基，或者Rc和Rd一起形成可选择地取代的碳环或可选择地取代的杂环；R1为OH、OR、NR'R'、NHC(=O)R、NHSO2R；R2为H、F、C1、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，可选择地取代的芳基或=O基团（与=O连接的碳形成羰基基团）；R3为H、OH、F、C1、Br、I、Cl、可选择地取代的C1-C20烷基、烯基或炔基（'烃基'），最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基，使得R3连接的碳具有R或S构型；R为H、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基，R'和R'各自独立地为H、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基；或者R'和R'一起形成可选择地取代的杂环，最好是4到7成员的可选择地取代的杂环基团或与R'和R'连接的氮原子形成可选择地取代的杂芳基环；其中所述化合物不含金属催化剂。
• [EN] QUINOLINES AS FGFR KINASE MODULATORS<br/>[FR] QUINOLINES COMME MODULATEURS DE LA FGFR KINASE
  申请人：ASTEX THERAPEUTICS LTD

  公开号：WO2013061074A1

  公开（公告）日：2013-05-02

  The invention relates to new quinoline derivative compounds of formula (I), to pharmaceutical compositions comprising said compounds, to processes for the preparation of said compounds and to the use of said compounds in the treatment of diseases, e.g. cancer. Formula (I)

  本发明涉及公式（I）的新喹啉衍生物化合物，包括含有该化合物的制药组合物，制备该化合物的方法以及利用该化合物治疗疾病，例如癌症。公式（I）
• [EN] FORMATION OF CHIRAL 4-CHROMANONES USING CHIRAL PYRROLIDINES IN THE PRESENCE OF ACIDS<br/>[FR] FORMATION DE 4-CHROMANONES CHIRALES À PARTIR DE PYRROLIDINES CHIRALES, EN PRÉSENCE D'ACIDES
  申请人：DSM IP ASSETS BV

  公开号：WO2015001027A1

  公开（公告）日：2015-01-08

  The present invention relates to a synthesis of chromanones or chromanes in a stereospecific matter in view of the 2-position in the chromanone or chromane ring. It has been found that this synthesis is particularly possible in the presence of a chiral compound of a specific type and of at least one Bransted acid or in the presence a specific chiral compound having a Bransted acid functional group in the molecule.

  本发明涉及在考虑到2-位置的立体特异性情况下合成香豆酮或香豆烷，发现在特定类型的手性化合物和至少一种布朗斯特酸的存在下，或在分子中具有布朗斯特酸官能团的特定手性化合物的存在下，这种合成特别可能实现。
• METHOD FOR PRODUCING FIVE-MEMBERED RING-CONTAINING COMPOUND
  申请人：Hayashi Yujiro

  公开号：US20140051874A1

  公开（公告）日：2014-02-20

  The present invention provides a method that allows production of stereospecific and asymmetrical five-membered ring-containing compounds serving as synthetic intermediates for formation of five-membered rings of prostaglandins and the like, with high yield and excellent stereoselectivity in terms of diastereoselectivity and enantioselectivity in a short process without requiring troublesome procedures such as optical resolution. The method for producing a five-membered ring-containing compound includes a cyclization step of condensing and cyclizing an α,β-unsaturated nitro compound represented by the following chemical formula (I) with a 1,4-butanedione compound, in the presence of a catalyst formed by a compound having a pyrrolidine ring and an optically active α-carbon relative to the nitrogen on the ring, in a water-insoluble organic solvent and/or a non-oxygen atom-containing water-soluble organic solvent so as to produce the five-membered ring-containing compound represented by the following chemical formula (II).

  本发明提供了一种方法，允许生产立体特异性和非对称的含五元环化合物，作为合成前体，用于形成前列腺素等含五元环的化合物，该方法在短时间内以高产率和卓越的立体选择性（包括对映选择性和对映异构选择性）进行，而无需进行繁琐的光学分辨过程。生产含五元环化合物的方法包括以下化学式（I）所表示的α，β-不饱和硝基化合物与1,4-丁二酮化合物缩合和环化的环化步骤，在具有吡咯烷环和具有环上氮原子的光学活性α-碳的化合物形成的催化剂存在下，在不溶于水的有机溶剂和/或不含氧原子的水溶性有机溶剂中，以生产以下化学式（II）所表示的含五元环化合物。
• [EN] NOVEL SYNTHESIS OF INTERMEDIATES FOR THE PREPARATION OF ALPHA-TOCOPHEROL<br/>[FR] NOUVELLE SYNTHÈSE D'INTERMÉDIAIRES DESTINÉS À LA PRÉPARATION D'ALPHA-TOCOPHÉROL
  申请人：DSM IP ASSETS BV

  公开号：WO2019012000A1

  公开（公告）日：2019-01-17

  The present invention relates to a novel synthetic pathway for alpha- tocopherol. The invention discloses different reactions yielding some new intermediates in a very high yield and stereoselectivity.

  本发明涉及一种新型合成途径，用于合成α-生育酚。该发明揭示了不同的反应，产生了一些新的中间体，其收率和立体选择性非常高。