Gold-catalysed regioselective cascade cycloisomerisation reactions of aza-enediynes for the synthesis of substituted benzoisoquinoline derivatives

Undeela, Sridhar; Chandra, Rajesh; Nanubolu, Jagadeesh Babu; Menon, Rajeev S.

doi:10.1039/c8ob02544d

Cited by 9 publications

(3 citation statements)

References 40 publications

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“…Most recently, Menon and co-workers reported a goldcatalyzed regioselective cascade cycloisomerization reaction of aza-enediynes 89, affording substituted dihydrobenzo[f]isoquinoline derivatives 90 in excellent yields (Scheme 16). 29 The authors postulated the following reaction mechanism: aza-enediynes 89 underwent gold-catalyzed propargyl-Claisen rearrangement, providing a -allenyl imine 91. Subsequent tautomerization proceeded via 1,3-hydride shift followed by a 6-aza-electrocyclization to yield dihydropyridine 93.…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Tertiary Enamides as Versatile and Valuable Substrates to Reach Chemical Diversity

Beltran

Miesch

2020

Synthesis

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Tertiary enamides display versatile reactivity and great stability compared to their enamine congeners. This review covers progress made in the development of new methods involving the enaminic reactivity of tertiary enamides with respect to the synthesis of complex nitrogen-containing compounds. A focus on the preparation of biologically active molecules is also presented. The syntheses reported herein are classified based on their reaction type. In addition, mechanistic insights are given for most of the new transformations.1 Introduction2 [2+2] Cycloadditions3 [4+2] Cycloadditions4 Electrocyclizations and Cycloisomerizations5 Sigmatropic Rearrangements6 Nucleophilic Additions7 Tertiary Enamides as Electrophiles8 Cross-Coupling Reactions9 Tertiary-Enamide-Assisted Reactions10 Conclusion and Perspectives

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Section: Short Review Syn Thesismentioning

confidence: 99%

Tertiary Enamides as Versatile and Valuable Substrates to Reach Chemical Diversity

Beltran

Miesch

2020

Synthesis

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“…33 Further studies by Alabugin et al, delved into the dual -Au(I)catalyzed Bergman cyclization, and provided useful insights into the nature of 1,4-zwitterionic species. 34,35,36,37 From this perspective, we envisioned polyenynes consisting of -Au(I)-acetylide and boronyl groups, which could be fine-tuned to undergo the desired cascade polymerization with high 6endo selectivity (Figure 2, bottom right). As has been shown before, the potential energy surface (PES) of concerted pericyclic rearrangements (Figure 3, A) can evolve into an interrupted (Figure 3, C) or in certain cases aborted (Figure 3, D) process under the influence of transition metal or the FLPs (Frustrated Lewis pair).…”

Section: Introductionmentioning

confidence: 99%

Zwitterionic Bergman-Triggered Cascade Polymerization: A Plateau Reaction Leading to Metal-Graphene Nanoribbon Semiconductors Using Boron-Metal Couple

Vidhani

Ubeda

Sautie

et al. 2022

Preprint

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With a rapid growth in artificial intelligence, designing high-speed and low power semiconducting material is of utmost importance. This investigation provides a theoretical basis to access covalently-bonded transition metal-graphene nanoribbon (TM-GNR) hybrid semiconductors whose DFT-computed bandgaps were much narrower than the commonly used pentacene. A systematic optimization of substrates containing remotely-placed boronyl groups and the transition metals produced the zwitterions via ionic Bergman cyclization (i-BC) and unlocked the polymerization of metal-substituted polyenynes. Aside from i-BC, the subsequent steps showed plateau-TS involving structureless transition regions. A multivariate analysis revealed a strong dependence of activation energy and the cyclization mode on the electronic nature of boron and Au(I). Consequently, three regions corresponding to radical Bergman (r-BC), ionic Bergman (i-BC), and ionic Schreiner-Pascal (i-SP) cyclizations were identified. The boundaries between these regions corresponded to the mechanistic shift induced by three-center-three-electron (3c-3e) hydrogen bond, three-center-four-electron (3c-4e) hydrogen bond, and vacant p-orbital on boron. The ideal combination for cascade polymerization was observed near the boundary between i-BC and i-SP.

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“…2, bottom left) 33 , which is not a feature of the dual σ,π-Au(I)-catalyzed protocol. Subsequently, Alabugin et al explored the dual σ,π-Au(I)-catalyzed Bergman cyclization, providing valuable insights into the nature of 1,4-zwitterionic species [34][35][36][37] .…”

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confidence: 99%

Zwitterionic Bergman cyclization triggered polymerization gives access to metal-graphene nanoribbons using a boron metal couple

et al. 2023

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With the rapid growth in artificial intelligence, designing high-speed and low-power semiconducting materials is of utmost importance. This investigation provides a theoretical basis to access covalently bonded transition metal-graphene nanoribbon (TM-GNR) hybrid semiconductors whose DFT-computed bandgaps were much narrower than the commonly used pentacene. Systematic optimization of substrates containing remotely placed boryl groups and the transition metals produced the zwitterions via ionic Bergman cyclization (i-BC) and unlocked the polymerization of metal-substituted polyenynes. Aside from i-BC, the subsequent steps were barrierless, which involved structureless transition regions. Multivariate analysis revealed the strong dependence of activation energy and the cyclization mode on the electronic nature of boron and Au(I). Consequently, three regions corresponding to radical Bergman (r-BC), ionic Bergman (i-BC), and ionic Schreiner-Pascal (i-SP) cyclizations were identified. The boundaries between these regions corresponded to the mechanistic shift induced by the three-center-three-electron (3c-3e) hydrogen bond, three-center-four-electron (3c-4e) hydrogen bond, and vacant p-orbital on boron. The ideal combination for cascade polymerization was observed near the boundary between i-BC and i-SP.

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Gold-catalysed regioselective cascade cycloisomerisation reactions of aza-enediynes for the synthesis of substituted benzoisoquinoline derivatives

Abstract: A facile, regioselective, gold-catalysed cascade cycloisomerisation of easily assembled aza-enediynes to afford dihydrobenzo[f]isoquinoline derivatives is reported.

Cited by 9 publications

References 40 publications

Tertiary Enamides as Versatile and Valuable Substrates to Reach Chemical Diversity

Tertiary Enamides as Versatile and Valuable Substrates to Reach Chemical Diversity

Zwitterionic Bergman-Triggered Cascade Polymerization: A Plateau Reaction Leading to Metal-Graphene Nanoribbon Semiconductors Using Boron-Metal Couple

Zwitterionic Bergman cyclization triggered polymerization gives access to metal-graphene nanoribbons using a boron metal couple

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