Benzylic Metallation of Thiobenzamides and Thionaphthamides

N-[(R)-1-Phenylethyl]thiobenzamide

“…Begum et al, 2006;Brunner et al, 1996). Thioamides especially can act as anionic monodentate or bidentate, chelating or bridging ligands after deprotonation, and they can also provide a potential source of axial chirality owing to their non-planarity (Ach et al, 2002;Artis & Lipton, 1998;Hossain et al, 2003;). In this paper, we report the synthesis and crystal structure of N-[(R)-1-phenylethyl]thiobenzamide (I), with an aim to subsequently investigate the axial chirality of its metal complexes.…”

Organic Synthesis with N‐Heterocyclic Carbenes of Indazole: Synthesis of Benzo(thio)imidates, Benzo[d][1,3]thiazines and Quinazoline‐4‐thiones

“…[43] Thionations can be performed by P 4 S 10 /silicon oil, [44] aqueous ammonium sulfide, [45] or polymer-supported thionation reagents. [46] Alternative approaches incompatible with preparation of benzamides as starting materials are addition reactions of aromatic Grignard reagents to isothiocyanates, [47] and the reaction of imines [48] or amines with sulfur under microwave conditions [49] which either fail or have never been applied to the synthesis of 2-anilinothioamides. The same is true for the hydrolysis of phosphorylated thiobenzamides, [50] preparations starting from aldehydes, benzotriazole, and unsubstituted thiobenzamide, [51] and substitution reactions of primary amines with benzocarbodithioesters.…”

Silylation and alkylation of thioamide dianions ofN-arylmethyl secondary thioamides, and reduction of the resulting thioamides leading to secondary and primary amines

“…As a result, the selective reduction of (3) proceeded in t-BuOMe to give (18) in 82% yield. The reduction of (4), (5), and (11) with LiAlH 4 took place in a similar way to give (19), (20), and (23), respectively, in good yields, whereas the reduction of (6) did not give the corresponding product (20) but rather gave complex mixtures, including (22). In contrast to these results, the reduction with LiAlH 4 could not be applied to thioamides bearing a pyridyl group (13)(14)(15)(16).…”

“…Many synthetic applications of thioamides have also been reported (11). As an example, the treatment of thioamides with bases gives various types of carbanions (12)(13)(14)(15)(16)(17)(18)(19)(20)(21). During the course of our studies on chalcogenoamides (22)(23)(24)(25)(26)(27)(28)(29)(30), we also found that the reaction of Nbenzyl secondary thioamides (1) with 2 equivalents of BuLi led to thioamide dianions (2) (31, 32) ( Figure 1).…”