Evidence for 2-fold hyperconjugation in the solvolysis of 5-(trimethylsilyl) and 5-(trimethylstannyl)-2-adamantyl sulfonates

Adcock, William; Coope, Janet; Shiner, V. J.; Trout, Neil A.

doi:10.1021/jo00292a002

Cited by 42 publications

(55 citation statements)

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“…Double hyperconjugation extends the delocalization range even further by placing a σ‐bridge between a donor and an acceptor. In chemistry of cations, this interaction has been called the δ‐effect and found experimentally to be significant for silicon and tin . Expansion of these studies to a larger set of cations found that, double hyperconjugation with a number of equatorial substituents can provide significant stabilization (R = AlH 2 , GaH 2 , GeH 3 , AsH 2 , SiH 3 , PH 2 , BH 2 , SeH, or destabilization (R = SH, Br, NH 2 , Cl, O, F) to the δ‐cyclohexyl cation with the equatorially oriented empty p‐orbital.…”

Section: Types 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: Types Of Hyperconjugationmentioning

confidence: 99%

Hyperconjugation

Alabugin

Gomes

Abdo

2018

WIREs Comput Mol Sci

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“…Double hyperconjugation extends the delocalization range even further by placing a σ‐bridge between a donor and an acceptor. In the chemistry of cations, this interaction has been called the δ‐effect and found experimentally to be significant for silicon and tin 115–117. Expansion of these studies to a larger set of cations118,119 showed that, double hyperconjugation with a number of equatorial substituents can provide significant stabilization (R = AlH 2 , GaH 2 , GeH 3 , AsH 2 , SiH 3 , PH 2 , BH 2 , SeH) or destabilization (R = SH, Br, NH 2 , Cl, O, F) to the δ‐cyclohexyl cation with the equatorially oriented empty p‐orbital (Figure 12, equatorial ‘hyperconjomer’, vide infra ).…”

Section: Types Of Hyperconjugationmentioning

confidence: 99%

Hyperconjugation

Alabugin

Gilmore

Peterson

2011

WIREs Comput Mol Sci

289

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This review outlines the ubiquitous nature of hyperconjugative interactions and their role 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 polarizibility. The danger of underestimating the magnitude of hyperconjugative interactions are illustrated by a number of spectroscopic, conformational, and structural effects. Through the use of advanced computational techniques, the true role of hyperconjugative effects, as it pertains to their influence on stereoelectronics, conformational equilibria, and reactivities relative to other electronic effects, continue to be uncovered.

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“…The tetrahedral intermediates 15-17 can readily achieve the correct geometry for the concerted breakdown shown in Scheme 3; similar types of fragmented products are formed in high yield in the solvolysis of the δ-trimethylstannyl esters 18 36 and 19 37 (Schemes 5 and 6). Whether the alkene products We were interested to see whether the ability of the trimethylstannyl substituent to promote the migration of the β-carbon in the Baeyer-Villiger reaction is dependent upon stereochemistry.…”

Section: Resultsmentioning

confidence: 98%