13092-79-0Relevant academic research and scientific papers
Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
Yi, Jaeeun,Kim, Hyun Tae,Jaladi, Ashok Kumar,An, Duk Keun
supporting information, p. 129 - 132 (2021/11/17)
Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
Hydroamination of unactivated alkenes catalyzed by novel platinum(II) N -heterocyclic carbene complexes
Cao, Peng,Cabrera, Jose,Padilla, Robin,Serra, Daniel,Rominger, Frank,Limbach, Michael
experimental part, p. 921 - 929 (2012/04/10)
Cationic platinum(II) complexes with bi- or tridentate (pincer) functionalized NHC ligands were found to be catalytically active in the hydroamination of unactivated alkenes. In some cases, the presence of water had an activating effect on the complexes. Reactions with the N-nucleophilic substrate morpholine led to a noncatalytic reaction in which the deprotonation product of the key cationic β-aminoalkyl platinum complex could be isolated and characterized. Surprisingly, attempted protonation of this complex did not give the expected N-alkylated product, indicating either the thermodynamic unfavorability of C-Pt bond cleavage or its kinetic inertness.
Towards supramolecular fixation of NOx gases: Encapsulated reagents for nitrosation
Kang, Yanlong,Zyryanov, Grigory V.,Rudkevich, Dmitry M.
, p. 1924 - 1932 (2007/10/03)
The use of simple calix[4]arenes for chemical conversion of NO2/ N2O4 gases is demonstrated in solution and in the solid state. Upon reacting with these gases, calixarenes 1 encapsulate nitrosonium (NO+) cations within their cavities with the formation of stable calixarene-NO+ complexes 2. These complexes act as encapsulated nitrosating reagents; cavity effects control their reactivity and selectivity. Complexes 2 were effectively used for nitrosation of secondary amides 5, including chiral derivatives. Unique size-shape selectivity was observed, allowing for exclusive nitrosation of less crowded N-Me amides 5a-e (up to 95% yields). Bulkier N-Alk (Alk > Me) substrates 5 did not react due to the hindered approach to the encapsulated NO+ reagents. Robust, silica gel based calixarene material 3 was prepared, which reversibly traps NO 2/ N2O4 with the formation of NO +-storing silica gel 4. With material 4, similar size-shape selectivity was observed for nitrosation. The N-Me-N-nitroso derivatives 6d,e were obtained with ～30% yields, while bulkier amides were nitrosated with much lower yields (+ species, which can be generated by a number of NOx gases, these supramolecular reagents and materials may be useful for NOx entrapment and separation in the environment and biomedical areas.
Encapsulated reagents for nitrosation
Zyryanov, Grigory V.,Rudkevich, Dmitry M.
, p. 1253 - 1256 (2007/10/03)
(Matrix presented) A novel class of stable, mild, and size-shape-selective nitrosating agents for secondary amides is introduced. These are based on reversible entrapment and release of reactive nitrosonium species by calix[4]arenes. The NO+ encapsulation controls the reaction selectivity.
Conversion of carbamates to amidosulfones and amides. Synthesis of the [14C]-labeled antiobesity agent Ro23-7637
White, James D.,Blakemore, Paul R.,Milicevic, Selena,Choudhry, Satish C.,Cupano, Joseph,Serico, Lucia
, p. 1803 - 1806 (2007/10/03)
Matrix presented Carbamates of primary and secondary amines react with the dianion of methyl phenyl sulfone to yield amidosulfones. Alylation of the amidosulfone followed by reductive removal of the sulfonyl residue gives an amide.
Photolytic Dehydrochlorination of N-Chloro-N-alkyl Amides: Formaton of N-(α-Methoxyalkyl) Amides
Phan, Xuan T.,Shannon, Paul J.
, p. 5164 - 5170 (2007/10/02)
The photoinduced dehydrochlorination, in methanol, of N-chloro-N-alkyl amides with one substitient at the α position to nitrogen gave good yields of N-(α-methoxyalkyl) amides and the parent amides as secondary products.N-Chloro amides disubstituted at the α position gave mostly parent amides.In most cases no products resulting from 1,5 hydrogen transfer of amidyl radicals were observed.The quantum yields of decomposition of N-chloro-N-methylpentanamide (1a) were significantly greater than unity, indicative of a chain process for dehydrochlorination.The reaction was affected by the solvent, addition of base or radical inhibitors, concentration of N-chloro amide, light intensity, and irradiation wavelenght.
