Highly Efficient One‐Step Synthesis of N‐Trimethylsiloxy Alkyl Imidothioates

Abstract

A hitherto unknown synthetic pathway for the synthesis of N‐trimethylsiloxy alkyl imidothioates has been presented. The catalyst‐free route uses a range of aromatic, aliphatic, and heterocyclic thiols in the presence of nitroalkanes and hexamethyldisilazane (HMDS). This unusual method expands upon the knowledge of nitro compounds and demonstrates their importance not only as solvents but also as valuable organic reagents. This reaction proceeds under mild conditions and is characterized by excellent yields and a facile workup.

Catalytic Formation of Silicon–Heteroatom (N, P, O, S) Bonds

“…On the other hand, it is important to stress that commercially available simple silylamines, such as N , O ‐bis(trimethylsilyl)acetamide (BSA) and 1,1,1,3,3,3‐hexamethyldisilazane (HMDS), are still the most useful in both organic and inorganic chemistry . In particular, HMDS seems to be a very interesting compound that has recently also been used in the preparation of phthalocyanines and porphyrazines, which are very important molecules from a biological point of view …”

Chemoselective Primary Amination of Aryl Boronic Acids by PIII/PV═O-Catalysis: Synthetic Capture of the Transient Nef Intermediate HNO

“…The foregoing preliminary experimental observations provide for a plausible pathway divided into two mechanistic phases, as depicted in Scheme . The first phase comprises the Nef decomposition of 1 to furnish HNO (Scheme A), gated by base-promoted activation of 2-nitropropane ( 1 ) by HMDS, forming silyl nitronate 6 . Hydrolysis of intermediate 6 via the intermediacy of hemiaminal 7 and nitroso acetal 8 leads ultimately to the formation of HNO ( 9 ).…”

“…The first phase comprises the Nef decomposition of 1 to furnish HNO (Scheme 1A), gated by base-promoted activation of 2-nitropropane (1) by HMDS, forming silyl nitronate 6. 43 Hydrolysis of intermediate 6 via the intermediacy of hemiaminal 7 and nitroso acetal 8 leads ultimately to the formation of HNO (9). In the second phase, HNO (9) thus formed engages P III species P5 and enters into the P III /P V O redox cycle (Scheme 1B).…”

Silicon–nitrogen bond formation via dealkynative coupling of amines with bis(trimethylsilyl)acetylene mediated by KHMDS

“…Silylamines are prevalent in organic chemistry, so new methods are needed for their synthesis. [1][2][3][4] Indeed, these compounds wherein the silyl moiety is directly bonded to nitrogen have found broad application, including the utilization as bases, 5 silylating agents (e.g., needed for the protection of reactive groups such as OH), [6][7][8] and ligands for several complexes (Figure 1, a). [9][10][11][12][13][14][15] Aminosilanes can be readily accessed via welldeveloped stoichiometric methods.…”

“…1–4 Indeed, these compounds wherein the silyl moiety is directly bonded to nitrogen have found broad applications, including their utilization as bases, 5 silylating agents ( e.g. , needed for the protection of reactive groups such as OH), 6–8 and ligands for several complexes (Fig. 1a).…”