Reactivity of 1-allylsilatrane in ruthenium-catalyzed silylative coupling with olefins – mechanistic considerations

Abstract

We have developed a new effective route for obtaining (E)-vinyl-substituted silatranes via ruthenium-catalyzed silylative coupling of 1-allylsilatrane with olefins. Experimental research allowed us also to propose the mechanism of the process based on stoichiometric reactions.

Direct Alkylative Reductive Amination using 1-Allylsilatrane

“…While not yet commercially available, 1-allylsilatrane can be synthesized from readily available starting materials on a multi-gram scale in high yields. [19][20][21][22] Herein, we report a metal-and fluoride-free procedure to access benzaldehyde-and aniline-derived homoallylic amines using 1-allylsilatrane. Scheme 1: Three component reactions to access homoallylic amines using allylsilanes.…”

Direct Alkylative Amination Using 1‐Allylsilatrane**

“…We envisioned it might be possible to intercept the imine intermediate instead with 1‐allylsilatrane to form new C−C bonds during the course of reductive amination and produce valuable building blocks that are amenable to further modifications. While not yet commercially available, 1‐allylsilatrane can be synthesized from readily available starting materials on a multi‐gram scale in high yields [14,23–25] . Corriu and coworkers demonstrated that allylsilatrane could serve as a masked C ‐nucleophile; [23] the other two accounts to‐date of using this tricyclic caged silane reagent in synthetic endeavors are the metal‐catalyzed coupling of 1‐allylsilatrane with styrene through a ruthenium precursor [14] and the allylation of pyridine via activation by Troc‐chloride in combination with halogen‐bonding driven catalysis [15] .…”

“…While not yet commercially available, 1-allylsilatrane can be synthesized from readily available starting materials on a multi-gram scale in high yields. [14,[23][24][25] Corriu and coworkers demonstrated that allylsilatrane could serve as a masked C-nucleophile; [23] the other two accounts to-date of using this tricyclic caged silane reagent in synthetic endeavors are the metal-catalyzed coupling of 1-allylsilatrane with styrene through a ruthenium precursor [14] and the allylation of pyridine via activation by Troc-chloride in combination with halogenbonding driven catalysis. [15] Herein, we report a metal-and fluoride-free procedure to access benzaldehyde-and anilinederived homoallylic amines using 1-allylsilatrane.…”