52384-47-1Relevant academic research and scientific papers
Efficient Co-Catalyzed Double Hydroboration of Nitriles: Application to One-Pot Conversion of Nitriles to Aldimines
Gudun, Kristina A.,Slamova, Ainur,Hayrapetyan, Davit,Khalimon, Andrey Y.
, p. 4963 - 4968 (2020)
The commercially available and bench-stable Co(acac)2/dpephos system is employed as a precatalyst for selective and efficient room temperature hydroboration of organic nitriles with HBPin to produce a series of N,N-diborylamines [RN(BPin)2], which react in situ with aldehydes to give aldimines. Formation of aldimines from N,N-diborylamines does not require a dehydrating agent, is applicable to a wide range of N,N-diborylamine and aldehyde substrates and is highly chemoselective, being unaffected by various common functional groups, such as alkenes, alkynes, secondary amines, ketones, esters, amides, carboxylic acids, pyridines, nitriles, and nitro compounds. The overall transformation represents a synthetically valuable approach to aldimines from nitriles and can be performed in a sequential one-pot manner, tolerating ester, lactone, carboxamide and unactivated alkene functionalities.
A cascade Aza-Cope/Aza-prins cyclization leading to piperidine derivatives
Nallasivam, Jothi L.,Fernandes, Rodney A.
, p. 2012 - 2022 (2015/03/18)
The cascade aza-Cope/aza-Prins cyclization of homoallylamines to give substituted piperidines has been explored. The use of glyoxalic acid as the carbonyl component afforded bicyclic structures as a result of the internal carboxylate anion trapping the intermediate cation. The unimolecular bis-, tris-, and tetrakis(homoallylamine)s efficiently delivered the appended bis-, tris- and tetrakis(piperidine-4-ol)s (tripod and crucifix shape, respectively) as new entities. The latter compound served as an excellent ligand in the Suzuki-Miyaura cross-coupling reaction to synthesize incrustoporin. The cascade aza-Cope/aza-Prins cyclization of homoallylamines to give substituted piperidines is described. A unimolecular tetrapiperidine derivative, which resulted from this strategy, was employed as a ligand in the Suzuki-Miyaura cross-coupling reaction of an α-iodobutenolide with an arylboronic acid in an efficient synthesis of incrustoporin and its analogues.
Synthesis and solid-state characterization of self-assembled macrocyclic molecular rotors of bis(dithiocarbamate) ligands with diorganotin(IV)
Torres-Huerta, Aaron,Rodriguez-Molina, Braulio,Hoepfl, Herbert,Garcia-Garibay, Miguel A.
, p. 354 - 362 (2014/02/14)
Two bis(dithiocarbamate) (bdtc) metallamacrocyclic compounds, 1 and 2, and the deuterated analogues 1-d8 and 1-d20 were readily prepared through self-assembly processes involving the corresponding secondary bis(diamines), with two equivalents each of CS2 and dimethyltin(IV) dichloride. Solid-state characterization using FTIR, PXRD, and TGA indicated that the solid phases of both macrocycles were amorphous solids. For compound 1, a crystalline phase could only be obtained in the form of a dichloromethane solvate; however, the corresponding crystal lattice was unstable and collapsed rapidly under ambient conditions. The bdtc ligands containing para-disubstituted phenylene (compound 1) and bicyclo[2.2.2]octane groups (compound 2) showed rotational motion within the macrocyclic assemblies in the solid state. For compound 1, the internal rotation of the phenylene groups was examined first by 13C NMR CPMAS spectroscopy using the 1-d20 derivative in which the hydrogen atoms of the pendant phenyl groups had been substituted with deuterium atoms and also by 2H NMR spin echo experiments using the 1-d8 derivative in which the rotating phenylene groups have been deuterated. Line shape analysis using a log-Gaussian distribution model indicated that the central phenylene rings experience fast 2-fold flip reorientations over the sp2-sp3 carbon atom axes, overcoming an activation energy of Ea = 10 kcal/mol with a preexponential factor A = 3.9 × 1014 s-1. For compound 2, the 13C CPMAS experiments suggested that the bicyclo[2.2.2]octane moieties also undergo fast internal dynamics, which is in agreement with the higher symmetry of these fragments when compared to the phenylene spacers.
