Face Selection in Addition and Elimination in Sterically Unbiased Systems

Kaselj, Mira; Chung, Wen-Sheng; Noble, W. J. Le

doi:10.1021/cr980364y

Cited by 63 publications

(31 citation statements)

References 210 publications

(261 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…154–159 The larger donor ability of CH bonds compared to that of σ CC bonds is the cornerstone of this model 160. This suggestion stimulated many experimental161–166 and theoretical167–169 studies.…”

Section: Factors Controlling Hyperconjugationmentioning

confidence: 93%

Hyperconjugation

Alabugin

Gilmore

Peterson

2011

WIREs Comput Mol Sci

288

289

View full text Add to dashboard Cite

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.

show abstract

Section: Factors Controlling Hyperconjugationmentioning

confidence: 93%

Hyperconjugation

Alabugin

Gilmore

Peterson

2011

WIREs Comput Mol Sci

288

289

View full text Add to dashboard Cite

show abstract

“…This TS ‐ a′ structure was found to be 9.9 kcal mol −1 higher in energy than TS ‐ a (see the http://www.wiley-vch.de/contents/jc_2002/2007/z604610_s.pdf). This large energy difference can be explained, at least in part, in terms of hyperconjugative effects, which can also serve as a basis for rationalizing the facial selectivity 13. In all TSs that lead to observed dimers, the Δ‐4,5 bond of one orthoquinol follows an approach anti to the σ C,C bond of the allylic methyl substituent at C6 of the other orthoquinol unit.…”

Section: Methodsmentioning

confidence: 99%

Total Synthesis of (+)‐Aquaticol by Biomimetic Phenol Dearomatization: Double Diastereofacial Differentiation in the Diels–Alder Dimerization of Orthoquinols with a C₂‐Symmetric Transition State

2007

View full text Add to dashboard Cite

The absolute configuration of (þ)-aquaticol (1 a) described in this Communication should be revised to 3S,10S,14R,23R as shown on the structure below and its accompanying ORTEP diagram (monoclinic, P2 1 , Flack factor = À0.2(2), CCDC-295794). (þ)-Aquaticol was derived from SIBX-mediated oxidation of (þ)-(R)-hydroxycuparene (3). We thank Professor John Porco and Suwei Dong (Boston University) for pointing out this issue.

show abstract

“…Other interpretations of facial selectivities have also been reviewed [174][175][176][177][178][179][180]. This asymmetry of the p orbitals, if it occurs along the trajectory of addition, is proposed to be generally involved in facial selection in sterically unbiased systems.…”

Section: Resultsmentioning

confidence: 99%

Orbitals in Chemistry

Inagaki¹

2010

Topics in Current Chemistry

View full text Add to dashboard Cite

Face Selection in Addition and Elimination in Sterically Unbiased Systems

Cited by 63 publications

References 210 publications

Hyperconjugation

Hyperconjugation

Total Synthesis of (+)‐Aquaticol by Biomimetic Phenol Dearomatization: Double Diastereofacial Differentiation in the Diels–Alder Dimerization of Orthoquinols with a C₂‐Symmetric Transition State

Orbitals in Chemistry

Contact Info

Product

Resources

About

Face Selection in Addition and Elimination in Sterically Unbiased Systems

Cited by 63 publications

References 210 publications

Hyperconjugation

Hyperconjugation

Total Synthesis of (+)‐Aquaticol by Biomimetic Phenol Dearomatization: Double Diastereofacial Differentiation in the Diels–Alder Dimerization of Orthoquinols with a C2‐Symmetric Transition State

Orbitals in Chemistry

Contact Info

Product

Resources

About

Total Synthesis of (+)‐Aquaticol by Biomimetic Phenol Dearomatization: Double Diastereofacial Differentiation in the Diels–Alder Dimerization of Orthoquinols with a C₂‐Symmetric Transition State