Recent advances in 8π electrocyclization reactions

Liu, Lei; Du, Luan; Li, Baosheng

doi:10.1039/d2cc04805a

Cited by 14 publications

(8 citation statements)

References 106 publications

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“…14,15 Well-known examples include the synthesis of butadienes from cyclobutenes, 16 the Nazarov cyclization, 17,18 the electrocyclization of hexatrienes to cyclohexadienes 19 and the electrocyclization of octatetraenes. 20 In contrast, the electrocyclization of heptatrienyl anions to cycloheptadienyl anions (20 to 21 in Figure 2) remains largely neglected.…”

Section: Introductionmentioning

confidence: 99%

The Electrocyclization of Heptatrienyl Anions

Orellana,

Komijani

2023

Synthesis

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The thermal electrocyclization of heptatrienyl anions is reviewed. We begin with a succinct background on the importance of cycloheptane rings in complex molecules and a brief survey of approaches to their synthesis. We also review the fundamental aspects of this electrocyclization manifold, relying on the Woodward–Hoffmann rules for pericyclic chemistry. Then we survey the literature, covering the burst of discovery in the late 1960s and early 1970s, and the more sporadic reports in from the 1990s to the present day.1 Introduction2 The Electrocyclization of Heptatrienyl Anions3 Discovery and Early Development (1964–1975)4 Recent Developments (1996–2023)5 Concluding Remarks

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Section: Introductionmentioning

confidence: 99%

The Electrocyclization of Heptatrienyl Anions

Orellana,

Komijani

2023

Synthesis

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“…[3] In addition, our group reported a DFT study on eight-electron electrocyclizations, [4] with special emphasis on substituent effects. Recently, Li et al [5] have published an extensive review including the latest advances of this reaction for the synthesis of seven-/eight-membered ring scaffolds. However, higherorder electrocyclizations have received somewhat less attention, in contrast with higher-order cycloadditions.…”

Section: Introductionmentioning

confidence: 99%

Higher‐Order Electrocyclizations in Biological and Synthetic Processes

de Cózar,

Arrieta,

Arrastia

et al. 2023

ChemPlusChem

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In general, electrocyclizations follow the Woodward‐Hoffmann's rules of conservation of orbital symmetry. These rules have been extensively verified in low‐order processes, both in thermal and photochemical reactions, up to eight π‐electrons. However, when the number of π‐electrons in the system increases, some deviations of that general rules can be found. This focused review highlights the main features of reported higher‐order electrocyclizations involving 10, 12, 14, 16 and 18 π‐electrons. Some of these examples constitute useful intermediates in the synthesis of biologically active compounds. When computational studies were not included in the reported examples, DFT calculations have been performed to be included in this review. Analysis of the respective pericyclic topologies shows the importance of computational tools for understanding the selectivity observed experimentally.

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“…1d, we speculated that the metal-catalyzed 5-endoannulization of pyridine-alkyne might form zwitterionic vinyl metal species [27][28][29][30][31][32][33][34][35][36][37][38][39][40] that might resonate to become a reactive conjugated 8π electronic system and a metal carbene. [41][42][43] Electrocyclization reactions [44][45][46][47][48][49] can be driven by heating and are not affected by external conditions. However, the reactivity of metal carbene is closely related to the reaction system.…”

Section: Introductionmentioning

confidence: 99%

Divergently Access N-center 5,6,7-Perifused Cycle

Han

Yue

et al. 2023

Preprint

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Nitrogen-containing heterocycles are the key components in many pharmaceuticals and functional materials. In this study, we reported a transition metal-catalyzed high-order reaction sequence for synthesizing a structurally unique N-center 5,6,7-perifused cycle (NCPC). The key characteristics included the formation of a seven-membered ring by the 8π electrocyclization of various alkenes and aromatic heterocycles as π-components, in which metal carbene species generated that further induced the cleavage of the α-C-H or -C-C bond. Specifically, the latter could react with various nucleophilic reagents containing -O, -S, -N, and -C. The stereo-controlled late-stage modification of some complicated pharmaceuticals indicated the versatility of this protocol.

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Recent advances in 8π electrocyclization reactions

Abstract: Medium-ring systems, which constitute a class of structurally intriguing and biologically important molecules, are present in many natural products and pharmaceuticals. However, the construction of these skeletons is usually difficult...

Cited by 14 publications

References 106 publications

The Electrocyclization of Heptatrienyl Anions

The Electrocyclization of Heptatrienyl Anions

Higher‐Order Electrocyclizations in Biological and Synthetic Processes

Divergently Access N-center 5,6,7-Perifused Cycle

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