Ru‐catalyzed Formation of Thiosilanes and Selenosilanes using Dichalcogenides as a User‐Friendly Alternative to Thiols and Selenols

Abstract

A ruthenium-catalyzed reaction for the selective transformation of disulfides (and diselenides) into their silyl (and germyl) counterparts has been developed, as the first example of a thiol/thiolate-free protocol. Our strategy employs commercially available ruthenium dodecacarbonyl as the catalyst in combina-tion with user-friendly hydrosilanes (and hydrogermanes) and odorless dichalcogenides (S, Se). Further derivatization of heteroaryl halides into unsymmetrical sulfides demonstrated the synthetic potential of the obtained silylthioethers.

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

“…Notably, our initial studies ruled out the efficient silylation via dealkynative coupling (please see ref. 47 and 48). The main problem was related to the acidity of the amine.…”

“…Sustainable and eco-friendly synthetic approaches proceeded by main-group catalysis have gained recent significant attention. 39–44 On the basis of our recent success in activating silylacetylenes under sustainable catalysis, 45–48 we reasoned that an appropriate catalytic manifold could provide an efficient platform to generate diversified libraries of trimethylsilylated amines. In this communication, we report on the catalytic silylation of primary amines with bis(trimethylsilyl)acetylene (BTMSA) for the construction of N–Si bonds via dealkynative coupling, by using potassium bis(trimethylsilylamide) as the catalyst (Fig.…”

“…Given the fact of our previous studies concerning O–H and sp C–H silylation in the presence of KHMDS, 47,48 anilines with hydroxyl and ethynyl moieties were also examined (Scheme 4). For this purpose, an equimolar combination of BTMSA and bifunctional amines was subjected under our reaction conditions.…”

Access to germasiloxanes and alkynylgermanes mediated by earth-abundant species

“…This strategy has provided an entry point into various organogermanes including germasiloxanes and alkynylgermanes. Remarkably, not only KHMDS but also simple bases such as KOH can serve as efficient catalysts in this process.Organogermanium compounds are much less studied than their silicon counterparts, but very recently, an impetus to design new synthetic routes to various organogermanes was witnessed and significant contributions were reported [1][2][3][4][5][6][7][8][9][10][11] . That is not merely a scientific curiosity but primarily, the unique features of germanium compounds are the leading cause of this trend.…”

“…Organogermanium compounds are much less studied than their silicon counterparts, but very recently, an impetus to design new synthetic routes to various organogermanes was witnessed and significant contributions were reported [1][2][3][4][5][6][7][8][9][10][11] . That is not merely a scientific curiosity but primarily, the unique features of germanium compounds are the leading cause of this trend.…”