Design of Leaving Groups in Radical CC Fragmentations: Through‐Bond 2c–3e Interactions in Self‐Terminating Radical Cascades

Mondal, Sayantan; Gold, Brian; Mohamed, Rana K.; Alabugin, Igor V.

doi:10.1002/chem.201402843

Cited by 65 publications

(31 citation statements)

References 67 publications

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“…After a sequence of reactions that provide the formal 6‐endo‐trig product, the penultimate species of this cascade, the final step involves a C–C bond scission. The efficiency of fragmentation can be enhanced by stabilizing the rational design of radical leaving groups …”

Section: Spectroscopic Signatures Of Hyperconjugationmentioning

confidence: 99%

Hyperconjugation

Alabugin

Gomes

Abdo

2018

WIREs Comput Mol Sci

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This review outlines the role of hyperconjugative interactions in the structure and reactivity of organic molecules. After defining the common hyperconjugative patterns, we discuss the main factors controlling the magnitude of hyperconjugative effects, including orbital symmetry, energy gap, electronegativity, and polarizability. The danger of underestimating the contribution of hyperconjugative interactions are illustrated by a number of spectroscopic, conformational, and structural effects. The stereoelectronic nature of hyperconjugation offers useful ways for control of molecular stability and reactivity. New manifestations of hyperconjugative effects continue to be uncovered by theory and experiments. This article is categorized under: Structure and Mechanism > Molecular Structures Software > Molecular Modeling Structure and Mechanism > Reaction Mechanisms and Catalysis

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Section: Spectroscopic Signatures Of Hyperconjugationmentioning

confidence: 99%

Hyperconjugation

Alabugin

Gomes

Abdo

2018

WIREs Comput Mol Sci

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“…120 Substituted naphthalenes 84a,b were also obtained via a tin-mediated radical cyclization/fragmentation reaction occurring on dienynes 83a,b (Scheme 21b). 121,122 Benzofused enynals and enynones are valuable substrates in benzannulation processes under Lewis acid catalysis. Thus, naphthyl ketone 87 was prepared by the reaction of ortho-alkynyl benzaldehyde 85 with phenyl acetylene 86 in the presence of a catalytic amount of Au III Cl 3 (Scheme 22a).…”

Section: Synthesis Of Naphthalenesmentioning

confidence: 99%

(Hetero)aromatics from dienynes, enediynes and enyne–allenes

et al. 2016

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The construction of aromatic rings has become a key objective for organic chemists. While several strategies have been developed for the functionalization of pre-formed aromatic rings, the direct construction of an aromatic core starting from polyunsaturated systems is yet a less explored field. The potential of such reactions in the formation of aromatics increased at a regular pace in the last few years. Nowadays, there are reliable and well-established procedures to prepare polyenic derivatives, such as dienynes, enediynes, enyne-allenes and hetero-analogues. This has stimulated their use in the development of innovative cycloaromatizations. Different examples have recently emerged, suggesting large potential of this strategy in the preparation of (hetero)aromatics. Accordingly, this review highlights the recent advancements in this field and describes the different conditions exploited to trigger the process, including thermal and photochemical activation, as well as the use of transition metal catalysis and the addition of electrophiles/nucleophiles or radical species.

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“…We cannot rule out the pathway by which D abstracts the hydrogen from the solvent and regenerates A for the chain reaction. In addition, D undergoes a β‐scission ring‐opening process, driven by stabilizing the three‐electron “half‐bond” transition state, to produce the intermediate E which could be trapped by either TEMPO or the sulfonyl oxime ether reagent 7 , leading to the detection of the adduct 6 and 8 , respectively.…”

Section: Methodsmentioning

confidence: 99%

Selective Aerobic Oxygenation of Tertiary Allylic Alcohols with Molecular Oxygen

et al. 2019

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Aerobic epoxidation of tertiary allylic alcohols remains as ignificant challenge.R eported here is an efficient and highly chemoselective copper-catalyzed epoxidation and semipinacol rearrangement reaction of tertiary allylic alcohols with molecular oxygen. The solvent 1,4-dioxane activates dioxygen, therebyp recluding the addition of as acrificial reductant.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Design of Leaving Groups in Radical CC Fragmentations: Through‐Bond 2c–3e Interactions in Self‐Terminating Radical Cascades

Cited by 65 publications

References 67 publications

Hyperconjugation

Hyperconjugation

(Hetero)aromatics from dienynes, enediynes and enyne–allenes

Selective Aerobic Oxygenation of Tertiary Allylic Alcohols with Molecular Oxygen

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