Synthesis of 2-aminoazulene derivatives. Nucleophilic and palladium-catalyzed amination of 2-substituted azulene

Yokoyama, Ryuji; Ito, Shunji; Okujima, Tetsuo; Kubo, Takaya; Yasunami, Michio; Tajiri, Akio; Morita, Noboru

doi:10.1016/j.tet.2003.08.048

Cited by 24 publications

(9 citation statements)

References 32 publications

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“…In the presence of NaOtBu, Pd 2 (dba) 3 , and BINAP, the palladium‐catalyzed amination reaction of 2‐bromoazulene 19 c with amine derivatives 298 yielded the corresponding 2‐aminoazulenes 299 (Scheme 115, Table 14). [123] …”

Section: Pd‐catalyzed Functionalization Of Azulene Via Amination Reactionmentioning

confidence: 99%

Recent Advances in the Functionalization of Azulene Through Pd‐Catalyzed Cross‐Coupling Reactions

2021

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Azulene derivatives have important physical and physicochemical features, as well as advantageous biological qualities. The metal‐catalyzed processes have proven to be a highly practical method for azulene functionalization. The development in the synthesis of azulene derivatives, including (aryl)heteroaryl‐substituted and hetero‐fused azulene derivatives, through Pd‐catalyzed coupling techniques over the previous two decades is discussed in this research. Alkyl‐, alkenyl‐, and alkynylazulenes synthesized via Pd‐catalyzed cross‐coupling processes are also included.

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Section: Pd‐catalyzed Functionalization Of Azulene Via Amination Reactionmentioning

confidence: 99%

Recent Advances in the Functionalization of Azulene Through Pd‐Catalyzed Cross‐Coupling Reactions

2021

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“…11 in 86% yield (entry 9). Likewise, the reaction of 2 with piperidine produced 11 11 in 91% yield (entry 10). The reaction of 2 with pyrrolidine under the similar conditions gave 12 10 in 72% yield (entry 11).…”

Section: Nhmentioning

confidence: 99%

“…Previously, we have also demonstrated the 2-aminoazulene syntheses by both the S N Ar and Hartwig-Buchwald reaction by utilizing 2-bromoazulene (Scheme 1). 11 The procedure made the preparation of parent 2-aminoazulenes possible, but the synthesis of the 2bromoazulene precursor has some difficulty owing to relatively long reaction steps and low product yields. 12 For these reasons described above, development of a more general and practical method from readily available substrates is still expected for the preparation of 2-aminoazulene derivatives.…”

Section: Introductionmentioning

confidence: 99%

“…2-Aminoazulenes 13 and 14 with acyclic amine functions were obtained from 6 and 7 in 64% and 90% yields, respectively, by the similar manner (entry 4 and 5). The two-step synthesis of 13 11 and 14 should be one of the efficient procedures, since these compounds couldn't be obtained directly by the S N Ar reaction of 2 with the corresponding amines. On the other hand, deesterification of 8 and 9 led to decomposition, although the trace amount of starting materials was recovered.…”

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Synthesis of 2-amino- and 2-arylazoazulenes via nucleophilic aromatic substitution of 2-chloroazulenes with amines and arylhydrazines

et al. 2017

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The SAr reaction of 2-chloroazulene derivative 1 with ethoxycarbonyl groups at the 1,3-positions of the azulene ring with several amines afforded the corresponding 2-aminoazulenes 3-9 in excellent yields. 2-Chloroazulene (2) without the electron-withdrawing groups reacted with highly nucleophilic cyclic amines (i.e., morpholine, piperidine and pyrrolidine) under the high-temperature conditions in a sealed tube to produce the corresponding 2-aminoazulenes 10-12 in good yields. 2-Aminoazulenes 10-14 without the electron-withdrawing groups were also obtained in good yields by the treatment of compounds 3-7 with 100% HPO, but in the cases of the reaction of 8 and 9 with a secondary amine function, the decomposition of the products resulted. The synthesis of 2-arylazoazulenes 15-18 was also established via the SAr reaction of 1 with arylhydrazines. The optical and electrochemical properties of the 2-arylazoazulene derivatives were examined by UV/Vis spectroscopy, theoretical calculations and voltammetric experiments.

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“…3 In the chemistry of azulene, functionalization method for 2-position of azulene is mainly transition-metal-catalyzed because difficulty of electrophilic reaction. Thus, several applications of transition-mediated reactions, e.g., vinylation, 4 ethynylation, 5 and amination 6 utilizing azulenyl halides have appeared in the literature. We have also reported the palladium-catalyzed synthesis of various arylazulene derivatives.…”

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First Synthesis of 2-Heteroarylazulenes by the Electrophilic Substitution of Azulene with Triflate of N-Containing Heterocycles

Shoji¹,

Inoue²,

Ito³

et al. 2012

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-An efficient synthesis of 2-heteroarylazulene derivatives was established via electrophilic substitution. The reaction of 6-dimethylamino-1,3-di(methylthio)azulene (1a) with the triflate of N-containing heteroarenes proceeded in the presence of excess heteroarenes to afford the corresponding 2-dihydroheteroarylazulene derivatives 3−7. The 2-dihydroheteroarylazulene derivatives were readily converted into the desired 2-heteroarylazulene derivatives 8−11 by the treatment with KOH in alcohols in excellent yields, except for 4 and 5.Electrophilic substitution reactions are a very important and general methodology for the functionalization of aromatic compounds. In azulene derivatives, there are numerous reports for the electrophilic substitution reactions at the 1-and 3-positions of the azulene ring. Thus, functionalization for 2-position of azulene by electrophilic reaction is remained as a subject of azulene chemistry.In recent years, there has been intense interest in transition-metal-catalyzed carbon-carbon and carbon-heteroatom bond formation in aromatic compounds.

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Synthesis of 2-aminoazulene derivatives. Nucleophilic and palladium-catalyzed amination of 2-substituted azulene

Cited by 24 publications

References 32 publications

Recent Advances in the Functionalization of Azulene Through Pd‐Catalyzed Cross‐Coupling Reactions

Recent Advances in the Functionalization of Azulene Through Pd‐Catalyzed Cross‐Coupling Reactions

Synthesis of 2-amino- and 2-arylazoazulenes via nucleophilic aromatic substitution of 2-chloroazulenes with amines and arylhydrazines

First Synthesis of 2-Heteroarylazulenes by the Electrophilic Substitution of Azulene with Triflate of N-Containing Heterocycles

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