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Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule02:17

Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule

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If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
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A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
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Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

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The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
1.6K
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry01:28

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

3.1K
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
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ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

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All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
5.0K
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)01:30

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3.0K
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
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Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators
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Aromatic interactions as control elements in stereoselective organic reactions.

Elizabeth H Krenske1, K N Houk

  • 1School of Chemistry, University of Melbourne, VIC 3010, Australia. ekrenske@unimelb.edu.au

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Aromatic ring interactions, particularly CH-π interactions, significantly control stereoselectivity in organic reactions. Advanced quantum mechanical modeling reveals these attractive forces stabilize crowded transition states, guiding reaction outcomes.

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Area of Science:

  • Organic Chemistry
  • Computational Chemistry
  • Stereochemistry

Background:

  • Attractive interactions involving aromatic rings play a crucial role in chemical reactions.
  • Recent advancements in quantum mechanical modeling offer unprecedented detail in understanding these interactions.
  • Previous theories on stereoselectivity often overlooked the specific contributions of aromatic interactions.

Purpose of the Study:

  • To elucidate the influence of aromatic ring interactions on the stereoselectivity of various organic reactions.
  • To investigate the mechanistic details of cycloaddition reactions involving furan and oxyallyl intermediates.
  • To demonstrate the utility of transition-state modeling in predicting and controlling reaction stereochemistry.

Main Methods:

  • Utilizing quantum mechanical modeling to simulate ground-state and transition-state species.
  • Analyzing the energetic contributions of attractive interactions, such as CH-π interactions.
  • Comparing computational predictions with experimental observations for various reaction types.

Main Results:

  • Transition-state modeling identified CH-π interactions as key drivers of stereoselectivity in reactions like asymmetric dihydroxylations and cycloadditions.
  • For (4+3) cycloadditions, computations revealed that furan preferentially attacks via a more crowded transition state, stabilized by CH-π interactions.
  • This attractive interaction between aromatic rings and other functional groups was found to be a general principle controlling stereochemistry.

Conclusions:

  • Attractive interactions with aromatic rings, especially CH-π interactions, are critical for controlling stereoselectivity in a wide range of organic reactions.
  • Computational modeling provides powerful insights into reaction mechanisms and stereochemical outcomes.
  • The findings suggest a generalizable model for CH-π-directed stereocontrol in addition reactions involving aromatic substituents.