Related Experiment Video
Updated: Apr 1, 2026
07:06
A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
Published on: February 16, 2020
8.7K
Making Dimethylamino a Transformable Directing Group by Nickel-Catalyzed C-N Borylation
Hua Zhang1, Shinya Hagihara1, Kenichiro Itami2,3
1Institute of Transformative Bio-Molecules (WPI-ITbM) and, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602 (Japan).
Chemistry (Weinheim an Der Bergstrasse, Germany)
|October 6, 2015
Summary
Researchers developed a new nickel-catalyzed method to convert dimethylamino groups into other functionalities. This advance expands the utility of dimethylamino-containing molecules in organic synthesis.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- The dimethylamino (Me2N) group is a versatile functional group for directed aromatic functionalization.
- Existing methods for Me2N-directed reactions are expanding rapidly.
- A general method for transforming the Me2N group is lacking, limiting its synthetic applications.
Purpose of the Study:
- To develop a general method for transforming the dimethylamino group into other functionalities.
- To expand the synthetic utility of Me2N-containing organic molecules.
Main Methods:
- Nickel-catalyzed C-N borylation reactions.
- Utilized aryl- and benzyl-dimethylamines as substrates.
- Leveraged existing C-B functionalization methods.
Main Results:
- A novel nickel-catalyzed borylation of aryl- and benzyl-dimethylamines was achieved.
- This method allows the conversion of Me2N-containing molecules into diverse functional molecules.
- Demonstrated the transformation of a library of underutilized Me2N-containing compounds.
Conclusions:
- The reported C-N borylation provides a general method for Me2N group transformation.
- This methodology significantly broadens the applicability of Me2N-containing substrates in organic synthesis.
- Facilitates access to a wider range of functional molecules from readily available starting materials.
More Related Videos
Related Concept Videos
01:19Diazonium Group Substitution: –OH and –H
3.5K
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.
3.5K
01:19Amines to Amides: Acylation of Amines
3.8K
Various carboxylic acid derivatives (such as acid chlorides, esters, and anhydrides) can be used for the acylation of amines to yield amides. The reaction requires two equivalents of amines. The first amine molecule functions as a nucleophile and attacks the carbonyl carbon to produce a tetrahedral intermediate. This is followed by the loss of the leaving group and restoration of the C=O bond.
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
3.8K
01:11ortho–para-Directing Activators: –CH3, –OH, –NH2, –OCH3
8.0K
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...
8.0K
01:13meta-Directing Deactivators: –NO2, –CN, –CHO, –CO2R, –COR, –CO2H
7.1K
All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for...
7.1K
01:12Preparation of Nitriles
2.8K
One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...
2.8K
01:28Preparation of 1° Amines: Gabriel Synthesis
5.0K
Direct alkylation is not a suitable method for synthesizing amines because it produces polyalkylated products. Gabriel synthesis is the most preferred method to exclusively make primary amines. The method uses phthalimide, which contains a protected form of nitrogen that participates in alkylation only once to predominantly give primary amines.
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
5.0K