The Synthesis of Bicyclo [2,2,2]-2,5-octadiene<sup>1,2</sup>

Hine, Jack; Brown, John Angus; Zalkow, Leon H.; Gardner, William Elmore; Hine, Mildred

doi:10.1021/ja01608a022

Cited by 50 publications

(11 citation statements)

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“…That being said, Hine et al. still referred to phases in their text, i. e., by saying “overlapping lobes the same algebraic sign.” [154] But they then refer to atomic orbitals. Whatever confusion they had, their considerations were also in terms of molecular properties, not reactions.…”

Section: Orbitals With and Without Phases (And Nodes)mentioning

confidence: 99%

History of the Woodward‐Hoffmann Rules. The No‐Mechanism Puzzle**

Seeman

2022

The Chemical Record

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This is Paper 2 in the 27‐paper series on the history of the development of the Woodward‐Hoffmann rules. Paper 2 takes the reader back to the 1950s and early 1960s, before the publication of the first Woodward‐Hoffmann paper in January 1965. The scope of the pericyclic no‐mechanism problem is described along with many of the key “hints” or “clues” to orbital symmetry control that were available in the literature prior to 1965. A chronology of reactions with alternating stereospecificities is provided. A second chronology of alternating theoretical hints is provided, e. g., 4n+2 versus 4n. Another chronology is provided, that of the development of frontier molecular orbital theory, with and without phases and nodes. A tabulation is provided of 36 instances in which the MOs of 1,3‐butadiene were reported in the literature. A knowledge of the MOs of 1,3‐butadiene, plus a knowledge of some of the alternating stereospecific reactions, could have led many chemists to the solution of the pericyclic no‐mechanism problem before Woodward and Hoffmann.

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Section: Orbitals With and Without Phases (And Nodes)mentioning

confidence: 99%

History of the Woodward‐Hoffmann Rules. The No‐Mechanism Puzzle**

Seeman

2022

The Chemical Record

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“…Barrelene first caught attentioni n1 955 when Hine et al noted that this molecule might be aromatic. [5] Since the first synthesis of I by Zimmerman and Paufler in 1960, [4] this intriguingm olecule has been in focus of synthetic as well as theoretical chemists. [6] Involvement of barrelene type speciesh ave also been predicated in the activation of organic substrates with low-valent main group compounds.…”

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confidence: 99%

Distannabarrelenes with Three Coordinated Sn^II Atoms

Sharma

Glodde

Neumann

et al. 2020

Chemistry A European J

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Crystalline 1,4‐distannabarrelene compounds [(ADCAr)3Sn2]SnCl3 (3‐Ar) (ADCAr={ArC(NDipp)2CC}; Dipp=2,6‐iPr2C6H3, Ar=Ph or DMP; DMP=4‐Me2NC6H4) derived from anionic dicarbenes Li(ADCAr) (2‐Ar) (Ar=Ph or DMP) have been reported. The cationic moiety of 3‐Ar features a barrelene framework with three coordinated SnII atoms at the 1,4‐positions, whereas the anionic unit SnCl3 is formally derived from SnCl2 and chloride ion. The all carbon substituted bis‐stannylenes 3‐Ar have been characterized by NMR spectroscopy and X‐ray diffraction. DFT calculations reveal that the HOMO of 3‐Ph (ϵ=−6.40 eV) is mainly the lone‐pair orbital at the SnII atoms of the barrelene unit. 3‐Ar readily react with sulfur and selenium to afford the mixed‐valence SnII/SnIV compounds [(ADCAr)3SnSn(E)](SnCl6)0.5 (E=S 4‐Ar, Ar=Ph or DMP; E=Se 5‐Ph).

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“…The ethers 9 a and 9 b were thus prepared by O-methylation of 5 a and 5 b, respectively (Scheme 2). Treatment of 9 a and 9 b under the reducing conditions optimized for the preparation of 1 gave the carbo-barrelene 2 and partially reduced derivative 10 b of carbo-barrelene 3, [15] which were isolated with ca. 30 % and 17 % yield, respectively.…”

Section: Resultsmentioning

confidence: 99%

Carbo‐mer of Barrelene: A Rigid 3D‐Carbon‐Expanded Molecular Barrel

Zhu

Poater

Duhayon

et al. 2021

Chemistry A European J

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After extensive studies of 1D and 2D skeletal carbo-mers based on C 8 π-conjugating dialkynylbutatriene units (DABs:~C � CÀ (R)C=C = C=C(R)À C � C~) bridging sp or sp 2 centers in carbo-butene, carbo-xylylene or carbobenzene derivatives, 3D versions are envisaged through carbo-barrelenes and partially reduced derivatives thereof where two or three DAB blades span a bridge between sp 3 carbinol vertices or ether thereof. For R = Ph, stable representatives were synthesized through a pivotal [6] pericyclynedione, and extensively characterized by spectroscopic, electrochemical and crystallographic methods. Density functional theory calculations allow detailed analysis of structural and electronic features of the 7 Å high C 26 barrelshaped molecules, and show that they can behave as cages for ionic species. Beyond aesthetical concerns, the results could open prospects of applications in host-guest supramolecular chemistry and single molecule charge transport.

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The Synthesis of Bicyclo [2,2,2]-2,5-octadiene^1,2

Cited by 50 publications

References 5 publications

History of the Woodward‐Hoffmann Rules. The No‐Mechanism Puzzle**

History of the Woodward‐Hoffmann Rules. The No‐Mechanism Puzzle**

Distannabarrelenes with Three Coordinated Sn^II Atoms

Carbo‐mer of Barrelene: A Rigid 3D‐Carbon‐Expanded Molecular Barrel

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The Synthesis of Bicyclo [2,2,2]-2,5-octadiene1,2

Cited by 50 publications

References 5 publications

History of the Woodward‐Hoffmann Rules. The No‐Mechanism Puzzle**

History of the Woodward‐Hoffmann Rules. The No‐Mechanism Puzzle**

Distannabarrelenes with Three Coordinated SnII Atoms

Carbo‐mer of Barrelene: A Rigid 3D‐Carbon‐Expanded Molecular Barrel

Contact Info

Product

Resources

About

The Synthesis of Bicyclo [2,2,2]-2,5-octadiene^1,2

Distannabarrelenes with Three Coordinated Sn^II Atoms