Titanacarborane mediated C–N bond forming/breaking reactions

Synthesis of New Racemic α,α-Diaminocarboxylic Ester Derivatives

“…Among these, C-N bond formation is one of the most important transformations. The reactions of amines have been a topic of immense research interest due to their synthetic utility [ 29 , 30 , 31 , 32 , 33 ] and biological activity [ 34 ]. Amines are widely used as intermediates to prepare solvents, fine chemicals, agrochemicals, pharmaceuticals and as polymerization catalysts [ 35 , 36 , 37 ].…”

Mechanistic Study on the Cleavage and Reorganization of C(sp3)H and CN Bonds in Carbodiimides: Synthesis of 1,2‐Dihydrothiopyrimidines and 2,3‐Dihydropyrimidinthiones through Four‐Component Coupling

“…Thus, various 1,2-dihydrothiopyrimidines 8 could be readily obtained in the same manner by coupling terminal alkyne, elemental sulfur, carbodiimide, and an electrophile (EX). Summarized in Table 1 (entries [1][2][3][4][5][6][7][8][9][10][11][12][13][14] are representative results for the formation of 8. In addition to benzyl bromide, methyl ido-dide and allyl bromide could also act as suitable electrophiles to furnish compounds 8 a-d (entries [1][2][3][4].…”

“…Summarized in Table 1 (entries [1][2][3][4][5][6][7][8][9][10][11][12][13][14] are representative results for the formation of 8. In addition to benzyl bromide, methyl ido-dide and allyl bromide could also act as suitable electrophiles to furnish compounds 8 a-d (entries [1][2][3][4]. A wide range of terminal alkynes including 1) aromatic terminal alkynes with either electron-withdrawing or electron-donating substituents at the phenyl ring, 2) heteroaromatic alkynes, and 3) aliphatic alkynes, could all afford the corresponding 1,2-dihydrothiopyrimidines 8 e-n in good isolated yields (entries [5][6][7][8][9][10][11][12][13][14].…”

“…[1][2][3] Carbodiimides have, for a long time, been used as versatile reagents for organic synthesis, pharmaceutical chemistry, and organometallic chemistry. [4][5][6][7][8] However, the cleavage and reorganization of chemical bonds in carbodiimide molecules has rarely been explored.…”

β‐Diketiminatoytterbium aryloxides: synthesis, structural characterization, and catalytic activity for addition of amines to carbodiimides

“…Guanidines are the important structural motifs found in many biologically and pharmaceutically active compounds, and addition of amines to carbodiimides provides a convenient and atom‐economical approach to guanidines . Therefore, development of metal catalysts for catalytic addition of amines to carbodiimides has attracted increasing attention . However, only primary aliphatic amines and some cyclic aliphatic amines were shown to undergo direct addition to carbodiimides under harsh conditions .…”