Synthesis of cycl[3.2.2]azine and benzo[<i>g</i>]cycl[3.2.2]azine derivatives by use of the [2 + 8] cycloaddition reaction of indolizines and dimethyl acetylenedicarboxylate

Tominaga, Yoshinori; Shiroshita, Yoshihide; Kurokawa, Tomohiko; Gotou, H.; Matsuda, Yoshiro; Hosomi, Akíra

doi:10.1002/jhet.5570260243

Cited by 32 publications

(11 citation statements)

References 20 publications

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“…Indolizines 9a – c obtained by desulfurization of 2-MeS derivatives were converted to cyclazines [ 29 ]. First indolizine 10 substituted by functional groups was involved in cyclization with DMAD in 1974 [ 30 ].…”

Section: Cyclazines From Indolizines Via [8+2] Catalytic Cycloaddimentioning

confidence: 99%

“…Later, this methodology was used to construct cyclophanes by applying 2-MeS-3-CONH 2 substituted structures 11a , b [ 31 , 32 ]. Later 2-MeS-3-COOR derivatives were hydrolyzed and decarboxylated to 12a – c and converted to cyclazines [ 29 ]. A similar methodology was used to construct cyclazine from 2-MeS-7-NMe 2 -indolizine 13b : desulfurization gave 7-NMe 2 derivative 13a and the addition of DMAD gave corresponding cyclazine [ 2 ].…”

Section: Cyclazines From Indolizines Via [8+2] Catalytic Cycloaddimentioning

confidence: 99%

“…Tominaga showed that indolizines 47a , b having annelated benzene ring across the bond C7–C8 underwent [8+2] cycloaddition forming benzo[g]cycl[3.2.2]azines [ 29 , 67 ], Scheme 22 .…”

Section: Cycloaddition To Benzoindolizines: Synthesis Of Benzo Dermentioning

confidence: 99%

“…1.8-Annelatyed indolizines gave purple 3-vinyl adducts 91 with DBZA [ 46 ] which underwent further dehydrogenation without cyclization (see Scheme 9 ). Benzoindolizines 92 [ 29 ] and their aza-derivative 93 [ 88 ] even in presence of catalysis gave the adducts together with cyclazines. 2-Isopropenyl indolizine 94 after prolonged heating with DMAD gave the mixture of isomeric 3-vinyl derivatives [ 109 ].…”

Section: Understanding the Mechanism: Michael Adducts Hydrogenatmentioning

confidence: 99%

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Indolizines and Their Hetero/Benzo Derivatives in Reactions of [8+2] Cycloaddition

Бабаев

Шадрин

2021

Molecules

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Peculiarities of [8+2] cycloaddition of acetylenes to indolizines are reviewed. Especially mentioned are indolizines with leaving groups at positions 3 and 5. Cycloaddition to aza- and benzo derivatives are reviewed, as well as 1,10-cyclizations and processes leading to cyclazines where indolizines are intermediates. Mechanistic features (adducts and cycloadducts) and theoretical aspects (one- or two-steps mechanism) are reviewed.

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Section: Cyclazines From Indolizines Via [8+2] Catalytic Cycloaddimentioning

confidence: 99%

Section: Cyclazines From Indolizines Via [8+2] Catalytic Cycloaddimentioning

confidence: 99%

“…Tominaga showed that indolizines 47a , b having annelated benzene ring across the bond C7–C8 underwent [8+2] cycloaddition forming benzo[g]cycl[3.2.2]azines [ 29 , 67 ], Scheme 22 .…”

Section: Cycloaddition To Benzoindolizines: Synthesis Of Benzo Dermentioning

confidence: 99%

Section: Understanding the Mechanism: Michael Adducts Hydrogenatmentioning

confidence: 99%

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Indolizines and Their Hetero/Benzo Derivatives in Reactions of [8+2] Cycloaddition

Бабаев

Шадрин

2021

Molecules

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“…Cyclazines have been defined as unsaturated tricyclic systems held planar by a centrally positioned nitrogen atom. A series of cycl[3.2.2]azine and related compounds have been synthesized and theoretically investigated because of their potential chemical and biological use . Aromaticity is one of the most important concepts for the understanding of heterocyclic chemistry.…”

Section: Introductionmentioning

confidence: 99%

The Influence of Benzo‐Fusion on the Aromatic Pathways and Ring Currents of Cycl[3.2.2]azine

Mattursun

Kerim

2017

Journal of Heterocyclic Chem

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The effect of benzene ring fusion on the aromaticity of cycl[3.2.2]azine was studied by calculating topological resonance energy (TRE), the percentage topological resonance energy (%TRE), and magnetic resonance energy (MRE). The bond resonance energy (BRE) and circuit resonance energy (CRE) indices were used to estimate the local aromaticity. Our BRE and CRE results show that the central nitrogen atom plays a significant role both in the global and local aromaticity of the compounds in our study, and contrary to what has been reported in the literature, none of these compounds are peripheral π‐electronic systems. In the case of benzene ring‐fused derivatives, benzene ring(s) exhibit relatively larger local aromaticity and reduce the local aromaticity of the central portion of cycl[3.2.2]azine to a level comparable to a corresponding non‐benzene fused parent system. Ring current results predict that a strong diamagnetic current flows around the whole molecular perimeter. The diatropic bond current results, as computed here, are in good agreement with the observed 1H‐NMR chemical shifts of these compounds.

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References

1992

Chemistry of Heterocyclic Compounds: A Series of Monographs

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Synthesis of cycl[3.2.2]azine and benzo[g]cycl[3.2.2]azine derivatives by use of the [2 + 8] cycloaddition reaction of indolizines and dimethyl acetylenedicarboxylate

Abstract: ChemInform Abstract Hydrolysis of the diesters (VI) (9 examples; obtained from the bromides (I)) and subsequent decarboxylation provide the desired cyclazines (VII). Similarly, the benzocyclazines (X) are synthesized starting from the known salt (VIII).

Cited by 32 publications

References 20 publications

Indolizines and Their Hetero/Benzo Derivatives in Reactions of [8+2] Cycloaddition

Indolizines and Their Hetero/Benzo Derivatives in Reactions of [8+2] Cycloaddition

The Influence of Benzo‐Fusion on the Aromatic Pathways and Ring Currents of Cycl[3.2.2]azine

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