5-benzyloxy-2-(2,2-dibromo-vinyl)-phenylamine | 886853-78-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5-benzyloxy-2-(2,2-dibromo-vinyl)-phenylamine
• 英文别名: 5-benzyloxy-2-(2,2-dibromovinyl)-phenylamine；5-Benzyloxy-2-(2-2-dibromovinyl)-phenylamine；2-(2,2-dibromoethenyl)-5-phenylmethoxyaniline
• CAS: 886853-78-7
• 化学式: C₁₅H₁₃Br₂NO
• 分子量: 383.082
• InChiKey: ZYCZRWPQVMCEEV-UHFFFAOYSA-N

物化性质

• 熔点：
  93-94 °C
• 沸点：
  485.4±45.0 °C(Predicted)
• 密度：
  1.687±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  35.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-benzyloxy-2-(2,2-dibromo-vinyl)-phenylamine 在 palladium diacetate 、 potassium carbonate 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 甲苯 为溶剂， 反应 14.08h， 以84%的产率得到6-(benzyloxy)-2-bromo-1H-indole
  参考文献：
  名称：

  The Role of Reversible Oxidative Addition in Selective Palladium(0)-Catalyzed Intramolecular Cross-Couplings of Polyhalogenated Substrates: Synthesis of Brominated Indoles

  摘要：

  A Pd(0)-catalyzed C-N bond-forming reaction leading to the synthesis of brominated indoles is described. The use of the phosphine ligand PtBu3 is necessary for reactivity. It is proposed that the bulky ligand serves to prevent inhibition of the catalyst by facilitating reversible oxidative addition into the product C-Br bond. Intramolecular coupling of a vinyl bromide in the presence of an aryl iodide can take place, demonstrating unprecedented levels of selectivity.

  DOI：

  10.1021/ja1052335
• 作为产物：
  描述：

  在 三苯基氧化膦 、 tin(ll) chloride 作用下， 以 乙醇 为溶剂， 反应 0.75h， 以2.35 g的产率得到5-benzyloxy-2-(2,2-dibromo-vinyl)-phenylamine
  参考文献：
  名称：

  宝石-二卤代烯烃的高选择性串联交叉偶联，可高效高效地合成高官能度的吲哚。

  摘要：

  使用吲哚合成法的高效率的方法偕- dihalovinylaniline底物和有机硼试剂经由Pd催化的分子内串联胺化和分子间Suzuki偶联显影。芳基，烯基和烷基硼试剂均已成功使用，从而形成了一种通用的模块化方法。该反应耐受苯胺上的多种取代方式，从而导致吲哚类化合物的基团在C 2 -C 7处。铜和钯介导的1,2-二芳基吲哚顺序合成的正交方法开发了多种有机硼试剂的广泛应用。

  DOI：

  10.1021/jo701987r

文献信息

• Tandem Pd-Catalyzed Double C−C Bond Formation: Effect of Water
  作者：David I. Chai、Mark Lautens

  DOI：10.1021/jo900053b

  日期：2009.4.17

  A highly efficient water-accelerated palladium-catalyzed reaction of gem-dibromoolefins with a boronic acid via a tandem Suzuki−Miyaura coupling and direct arylation is reported. A wide range of aryl, alkenyl, and alkyl boronic acids, as well as a variety of substitution patterns on the phenyl ring, are tolerated. Additionally, mechanistic studies were conducted to ascertain the order of the couplings

  据报道，通过串联的Suzuki-Miyaura偶联和直接芳基化反应，宝石-二溴代烯烃与硼酸进行了高效的水促进钯催化反应。宽范围的芳基，烯基和烷基硼酸，以及苯环上的各种取代方式都可以使用。此外，进行了机械研究，以确定耦合的顺序以及水的作用。这项研究的结果表明，主要途径是Suzuki-Miyaura偶联/直接芳基化序列，水加速了Pd（0）的形成和Suzuki-Miyaura偶联。
• Screening Methods
  申请人：Lautens Mark

  公开号：US20080039625A1

  公开（公告）日：2008-02-14

  Disclosed are processes for the preparation of 2-substituted indole compounds wherein the 2-substituent comprises an R 4 group, wherein R 4 is selected from the group consisting of monocyclic aromatic, polycyclic aromatic, monocyclic heteroaromatic, polycyclic heteroaromatic, 1° alkyl, and alkenyl, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents, and wherein R 4 is bonded to the 2-position of the indole ring via a C—C bond; the process comprising reacting an orthogem-dihalovinylaniline compound of the formula (I): wherein Halo comprises Br, Cl, or I; each of the one or more R 1 is independently selected from the group consisting of H, fluoro, lower alkyl, lower alkenyl, lower alkoxy, aryloxy, lower haloalkyl, lower alkenyl, —C(O)O-lower alkyl, monocyclic or polycyclic aryl or heteroaryl moiety, or R 1 is an alkenyl group bonded so to as to form a 4- to 20-membered fused monocycle or polycyclic ring with the indole ring; all of which are optionally substituted with one or more suitable substituents at one or more substitutable positions; R 2 comprises H, alkyl, cycloalkyl, aryl, heteroaryl, aryl-loweralkyl-, or heteroaryl-loweralkyl-, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents; R 3 comprises H, alkyl, haloalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycle, aryl-(C 1-6 )alkyl-, or heteroaryl-loweralkyl-, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents; with an organoboron reagent selected from the group consisting of a boronic ester of R 4 , a boronic acid of R 4 , a boronic acid anhydride of R 4 , a trialkylborane of R 4 and a 9-BBN derivative of R 4 ; in the presence of a base, a palladium metal pre-catalyst and a ligand under reaction conditions effective to form the 2-substituted indole compound. Also disclosed are processes for the preparation of ortho-gem-dihalovinylaniline compounds. Novel compounds prepared by the processes and novel uses of the compounds are likewise disclosed.

  本发明涉及制备2-取代吲哚化合物的方法，其中2-取代基包括R4基团，其中R4从单环芳香族、多环芳香族、单环杂芳族、多环杂芳族、1°烷基和烯基中选择，所有这些基团都可以在一个或多个可替换的位置上用一个或多个适当的取代基替换，并且其中R4通过C-C键与吲哚环的2-位置结合；该方法包括将式（I）的正交二卤代乙烯基苯胺化合物与来自以下组的有机硼试剂反应：其中Halo包括Br、Cl或I；其中一个或多个R1各自独立地选择自H、氟、低烷基、低烯基、低烷氧基、芳氧基、低卤代烷基、低烯基、-C（O）O-低烷基、单环或多环芳基或杂芳基基团，或者R1是一个烯基团，通过与吲哚环形成一个4到20个成员的融合的单环或多环环，所有这些基团都可以在一个或多个可替换的位置上用一个或多个适当的取代基替换；R2包括H、烷基、环烷基、芳基、杂芳基、芳基-低烷基-或杂芳基-低烷基-，所有这些基团都可以在一个或多个可替换的位置上用一个或多个适当的取代基替换；R3包括H、烷基、卤代烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环、芳基-(C1-6)烷基-或杂芳基-低烷基-，所有这些基团都可以在一个或多个可替换的位置上用一个或多个适当的取代基替换；在碱、钯金属预催化剂和配体存在下，以有效的反应条件形成2-取代吲哚化合物。本发明还涉及制备正交二卤代乙烯基苯胺化合物的方法。本发明还涉及通过上述方法制备的新化合物以及化合物的新用途。
• Silver-Promoted Domino Pd-Catalyzed Amination/Direct Arylation: Access to Polycyclic Heteroaromatics
  作者：Christopher S. Bryan、Mark Lautens

  DOI：10.1021/ol801932z

  日期：2008.10.16

  Novel tetracyclic and pentacyclic indole derivatives can be prepared from readily available gem-dibromovinyl substrates in a single step by means of an efficient Pd-catalyzed domino Buchwald-Hartwig amination/direct arylation reaction. Enhanced reactivity and selectivity are obtained by the addition of silver salts.
• 2-SUBSTITUTED INDOLES, THEIR PRECURSORS AND NOVEL PROCESSES FOR THE PREPARATION THEREOF
  申请人：Lautens, Mark

  公开号：EP1817283A1

  公开（公告）日：2007-08-15
• [EN] 2-SUBSTITUTED INDOLES, THEIR PRECURSORS AND NOVEL PROCESSES FOR THE PREPARATION THEREOF<br/>[FR] INDOLES SUBSTITUES EN POSITION 2, LEURS PRECURSEURS ET NOUVEAUX PROCEDES DE PREPARATION ASSOCIES
  申请人：LAUTENS MARK

  公开号：WO2006047888A1

  公开（公告）日：2006-05-11

  [EN] Disclosed are processes for the preparation of 2-substituted indole compounds wherein the 2-substituent comprises an R₄ group, wherein R₄ is selected from the group consisting of monocyclic aromatic, polycyclic aromatic, monocyclic heteroaromatic, polycyclic heteroaromatic, 1° alkyl, and alkenyl, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents, and wherein R₄ is bonded to the 2-position of the indole ring via a C-C bond; the process comprising reacting an ortho­gem-dihalovinylaniline compound of the formula (I): wherein Halo comprises Br, Cl, or I; each of the one or more R₁ is independently selected from the group consisting of H, fluoro, lower alkyl, lower alkenyl, lower alkoxy, aryloxy, lower haloalkyl, lower alkenyl, -C(O)O-lower alkyl, monocyclic or polycyclic aryl or heteroaryl moiety, or R₁ is an alkenyl group bonded so to as to form a 4- to 20-membered fused monocycle or polycyclic ring with the indole ring; all of which are optionally substituted with one or more suitable substituents at one or more substitutable positions; R₂ comprises H, alkyl, cycloalkyl, aryl, heteroaryl, aryl-loweralkyl-, or heteroaryl-loweralkyl-, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents; R₃ comprises H, alkyl, haloalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycle, aryl-(C_1-6)alkyl-, or heteroaryl-loweralkyl-, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents; with an organoboron reagent selected from the group consisting of a boronic ester of R₄, a boronic acid of R₄, a boronic acid anhydride of R₄, a trialkylborane of R₄ and a 9-BBN derivative of R₄; in the presence of a base, a palladium metal pre-catalyst and a ligand under reaction conditions effective to form the 2-substituted indole compound. Also disclosed are processes for the preparation of ortho-gem-dihalovinylaniline compounds. Novel compounds prepared by the processes and novel uses of the compounds are likewise disclosed.
  [FR] La présente invention se rapporte à des procédés de préparation de composés indoles substitués en position 2, le substituant en position 2 contenant un groupe R₄, R₄ étant sélectionné parmi les groupes aromatiques monocycliques, aromatiques polycycliques, hétéroaromatiques monocycliques, hétéroaromatiques polycycliques, alkyle 1° et alcényle, tous lesdits groupes étant éventuellement substitués à une ou plusieurs positions substituables par un ou plusieurs substituants appropriés, et R₄ étant lié à la position 2 du cycle indole par l'intermédiaire d'une liaison C-C. Le procédé selon l'invention consiste à faire réagir un composé d'ortho-gem-dihalovinylaniline représenté par la formule (I) avec un réactif d'organo-bore sélectionné parmi un ester boronique de R₄, un acide boronique de R₄, un anhydride d'acide boronique de R₄, un trialkylborane de R₄ et un dérivé 9-BBN de R₄, en présence d'une base d'un précatalyseur au palladium et d'un ligand dans des conditions de réaction permettant de former le composé indole substitué en position 2. Dans ladite formule (I) : Halo contient Br, Cl ou I ; chaque R₁ est sélectionné indépendamment parmi H, fluoro, alkyle inférieur, alcényle inférieur, alcoxy inférieur, aryloxy, haloalkyle inférieur, alcényle inférieur, alkyle inférieur-C(O)O, un groupe fonctionnel aryle ou hétéroaryle monocyclique ou polycyclique, ou R₁ est un groupe alcényle lié de manière à former un anneau monocyclique ou polycyclique fusionné à 4 à 20 éléments avec le cycle indole, tous ces derniers étant éventuellement substitués à une ou plusieurs positions substituables par un ou plusieurs substituants appropriés ; R₂ représente H, alkyle, cycloalkyle, aryle, hétéroaryle, aryle-alkyle inférieur, ou hétéroaryle-alkyle inférieur, tous ces derniers étant éventuellement substitués à une ou plusieurs positions substituables par un ou plusieurs substituants appropriés ; R₃ représente H, alkyle, haloalkyle, alcényle, alcynyle, aryle, hétéroaryle, cycloalkyle, hétérocycle, aryle-alkyle C_1-6, ou hétéroaryle-alkyle inférieur, tous ces derniers étant éventuellement substitués à une ou plusieurs positions substituables par un ou plusieurs substituants appropriés. L'invention concerne également des procédés de préparation de composés d'ortho-gem-dihalovinylaniline, ainsi que de nouveaux composés préparés à l'aide des procédés selon l'invention et de nouvelles utilisations desdits composés.