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Diazonium Group Substitution: –OH and –H01:19

Diazonium Group Substitution: –OH and –H

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Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
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[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

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The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
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Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
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Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

Cycloaddition Reactions: MO Requirements for Photochemical Activation

2.2K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview01:07

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In the presence of an aqueous base and a halogen, primary amides can lose the carbonyl (as carbon dioxide) and undergo rearrangement to form primary amines. This reaction, called the Hofmann rearrangement, can produce primary amines (aryl and alkyl) in high yields without contamination by secondary and tertiary amines.
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ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3

6.5K
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...
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Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
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Photoinduced ynamide structural reshuffling and functionalization.

Mohana Reddy Mutra1, Jeh-Jeng Wang2,3

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|April 29, 2022
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This study demonstrates photoinduced radical-triggered ynamide bond cleavage for synthesizing challenging chalcogen-substituted indoles. This method offers regio- and chemoselective control, avoiding harsh conditions and producing valuable N-heterocyclic compounds.

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Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry
  • Heterocyclic Chemistry

Background:

  • Ynamide radical chemistry is crucial for N-heterocyclic compound synthesis.
  • Challenges include high reactivity, byproducts, and poor selectivity.
  • Ynamide C(sp)-N bond fission is a persistent synthetic hurdle.

Purpose of the Study:

  • To achieve regio- and chemoselective ynamide bond fission using photoinduced radical triggers.
  • To develop a method for synthesizing challenging chalcogen-substituted indole derivatives.
  • To explore structural reshuffling and functionalization of 2-alkynyl-ynamides.

Main Methods:

  • Photoinduced radical reaction initiation.
  • Utilizing 2-alkynyl-ynamides as substrates.
  • Employing sulfone radicals for structural rearrangement.

Main Results:

  • Successful regio- and chemoselective ynamide bond cleavage.
  • Synthesis of previously inaccessible/challenging chalcogen-substituted indoles.
  • Efficient generation of multiple new bonds (N-C, C-C, C-S, C-X) under mild conditions.

Conclusions:

  • Photoinduced radical chemistry provides a novel pathway for ynamide C(sp)-N bond cleavage.
  • Sulfone radicals play a key role in the observed ynamide structural reshuffling.
  • The developed method offers excellent step/atom economy, broad scope, and scalability.