N-benzyl-N-(2-bromo-2-propen-1-yl)-N-(2-propen-1-yl)amine | 160929-07-7

• 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: N-benzyl-N-(2-bromo-2-propen-1-yl)-N-(2-propen-1-yl)amine
• 英文别名: N-allyl-N-benzyl-2-bromoallylamine；N-benzyl-2-bromo-N-prop-2-enylprop-2-en-1-amine
• CAS: 160929-07-7
• 化学式: C₁₃H₁₆BrN
• 分子量: 266.181
• InChiKey: CIZQULQGMWIGCB-UHFFFAOYSA-N

物化性质

• 沸点：
  292.0±28.0 °C(Predicted)
• 密度：
  1.236±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-benzyl-N-(2-bromo-2-propen-1-yl)-N-(2-propen-1-yl)amine 在 叔丁基锂 作用下， 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  5-exo versus 6-endo intramolecular carbolithiation of N-allyl-N-(2-lithioallyl)amines

  摘要：

  N-Allyl-N-(2-lithioallyl)amines undergo intramolecular carbometallation via 5-exo or 6-endo addition. The course of the reaction depends on the nitrogen electron density. 3-Functionalized-4-methylenepyrrolidines can be synthesized. (C) 1997 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00465-6
• 作为产物：
  描述：

  N-(2-bromoallyl)benzylamine 、 3-溴丙烯 在 三乙胺 作用下， 以 乙腈 为溶剂， 反应 18.0h， 生成 N-benzyl-N-(2-bromo-2-propen-1-yl)-N-(2-propen-1-yl)amine
  参考文献：
  名称：

  Suppressed β-Hydride Elimination in Palladium-Catalyzed Cascade Cyclization−Coupling Reactions:  An Efficient Synthesis of 3-Arylmethylpyrrolidines

  摘要：

  A novel type of palladium-catalyzed cascade cyclization-coupling reaction that proceeds with suppressed beta-hydride elimination has been found. One of the N-sulfonyl oxygens is suggested to coordinatively stabilize an alkylpalladium intermediate, thus preventing the intermediate from the usual beta-elimination, This is the first sequential palladium-catalyzed coupling reaction where the Suzuki and Heck reactions can compete. The reaction provides an efficient synthetic route to 4-methylene-3-arylmethylpyrrolidines, which are not readily available by other routes.

  DOI：

  10.1021/ol0056426

文献信息

• Intramolecular Heck-type reactions in aqueous medium. Dramatic change in regioselectivity
  作者：Sandrine Lemaire-Audoire、Monique Savignac、Christophe Dupuis、Jean-Pierre Genêt

  DOI：10.1016/0040-4039(96)00253-5

  日期：1996.3

  Efficient intramolecular Heck-type cyclizations were carried out in aqueous medium using water-soluble Pd/TPPTS catalysts. Under these conditions, the generally observed exo process was reversed in favor of the regioselective formation of endo cyclized compounds.

  使用水溶性Pd / TPPTS催化剂在水性介质中进行高效的分子内Heck型环化反应。在这些条件下，通常观察到的外切过程被逆转，有利于内环化化合物的区域选择性形成。
• Convenient Synthesis of Heterobicycles by Domino Heck−Diels−Alder Reactions
  作者：Laxminarayan Bhat、Arno G. Steinig、Ruth Appelbe、Armin de Meijere

  DOI：10.1002/1099-0690(200105)2001:9<1673::aid-ejoc1673>3.0.co;2-g

  日期：2001.5

  Palladium(0)-catalyzed intramolecular cross coupling of bromodialkenylamines, bromoalkenylalkenamides and bromodialkenyl ethers followed by in situ [4+2] cycloaddition with suitable dienophiles gave tetrahydroisoindolines (31−73% yield), tetrahydroisoindolin-1-ones (43−51%) and hexahydrobenzo[c]furans (35−55%), and hexahydro-1H-[2]pyrindines (66−75%), respectively, each in one-pot operations.

  钯 (0) 催化的溴二烯基胺、溴烯基烯酰胺和溴二烯基醚的分子内交叉偶联，然后与合适的亲二烯体进行原位 [4+2] 环加成，得到四氢异吲哚啉（31-73% 产率），四氢异吲哚-1-酮（43%）和六氢苯并 [c] 呋喃 (35-55%) 和六氢-1H-[2] 吡啶 (66-75%) 分别在一锅操作中。
• Zirconium-promoted intramolecular cyclization of terminal alkynes and unusual carbonylation reaction
  作者：José Barluenga、Roberto Sanz、Francisco J. Fañanás

  DOI：10.1039/c39950001009

  日期：——

  N-(2-bromoallyl)-N-prop-2-ynyl- and N-allyl-N-(2-bromoallyl)-amines 1 and 5 undergo intramolecular cyclization by sing zirconocene methyl chloride to give zirconacycles 4 and 6, respectively, which are characterized by deuteriolysis affording products 2 and 7; carbonylation of 6 and further reaction with electrophiles (deuterium oxide, allyl bromide, 4-chlorobenzonitrile, benzaldehyde, benzophenone and benzylideneaniline) leads to compounds 8, 9 and 11–15.

  N-(2-溴烯丙基)-N-丙-2-炔基-和N-烯丙基-N-(2-溴烯丙基)-胺1和5通过单-二茂锆甲基氯进行分子内环化，分别得到锆环4和6，其特点是氘解产生产物2和7；6的羰基化以及与亲电试剂（氘化氢、烯丙基溴、4-氯苯甲腈、苯甲醛、二苯甲酮和苯亚甲基苯胺）的进一步反应，得到化合物8、9和11-15。
• Zirconium-Mediated Intramolecular Coupling of Terminal Alkynes and Their Subsequent Carbonylation: Novel Synthesis of Seven- and Eight-Membered Heterocycles
  作者：José Barluenga、Roberto Sanz、Francisco J. Fañanás

  DOI：10.1002/chem.19970030820

  日期：1997.8

  AbstractThe development of a new method for the intramolecular coupling of terminal alkynes and for the synthesis of seven‐ and eight‐membered benzoheterocycles is reported. The key steps involve the generation of zirconocene‐alkyne complexes from 2‐bromoalkenes and the subsequent intramolecular carbometalation of olefins or acetylides. The 8‐unsubstituted zirconabicyclopentenes were carbonylated to afford unexpected products and allow access to polyfunctionalized molecules from simple starting materials.
• Nitrogen Assistance in Intramolecular Nickel-Promoted Tandem Cyclization−Quenching Processes
  作者：Daniel Solé、Yolanda Cancho、Amadeu Llebaria、Josep M. Moretó、Antonio Delgado

  DOI：10.1021/jo960677y

  日期：1996.1.1

  A diastereoselective and mild cyclization-quenching process based on the treatment of nitrogen-tethered halodienes with stoichiometric Ni(COD)(2) is described. The success of this methodology relies on the presence of a distal amino group capable of coordinating with the metal in the transient vinyl or alkylnickel species, thus controlling the diastereoselectivity of the cyclization step and preventing Ni-H beta-elimination prior to the quenching, In general, better results are obtained in cyclizations taking place via a 5-exo-trig process, and a diversity of mono- and bicyclic nitrogenated systems are afforded in high yields by the proper choice of starting halodienes and quenching reagents, The presence of 2,2'-bipyridine as a ligand results in an acceleration of the process, and in some cases, higher diastereoselectivities and/or supression of the Ni-H beta-elimination are observed.