Organosilicon reagents are highly versatile and privileged scaffolds in modern synthetic chemistry, largely due to the range of transformations the groups are amenable to. The β‐Silicon effect is one of the fundamental phenomena underpinning the inherent reactivity of organosilicon reagents, allowing unsaturated organosilanes to undergo a range of electrophilic substitutions with a variety of nucleophiles. The application of the β‐Silicon effect in a range of organic transformations is reviewed with the discussion divided up based on the class of silane. The reactivity of these compounds towards carbon, heteroatom and metallic electrophiles is discussed from classical applications such as the Sakurai allylation to contemporary applications such as cross‐coupling chemistry. In addition, examples of these transformations in the context of methodology development and natural product synthesis are provided.
We describe, for the first time, a highly regioselective hydrosilylation of propargylic amines. The reaction utilizes a PtCl 2 /XantPhos catalyst system to deliver hydrosilanes across the alkyne to afford multifunctional allylic amines in high yields. The reaction is tolerant to a wide variety of functional groups and provides high value intermediates with two distinct functional handles. The synthetic applicability of the reaction has been shown through the synthesis of diverse ambiphilic aziridines.Letter pubs.acs.org/OrgLett
An aza-Peterson olefination methodology to access 1,3-dienes and stilbene derivatives from the corresponding allyl- or benzyl trimethylsilanes is described. Silanes can be deprotonated using Schlosser’s base and added into N-phenyl imines or ketones to directly give the desired products in high yields.
The regio and stereoselective hydrosilylation of a variety of homopropargylic scaffolds is described. The reaction is tolerant to a variety of sterically and electronically varied substrates, affording only the E-vinyl...
We present the first study on the application of platinum complexes in the hydrostannylation of terminal alkynes. A range of platinum complexes were screened, with PtCl 2 /XPhos proving to provide the best selectivity for the β-(E)-vinyl stannane. The catalyst system is able to provide the corresponding vinyl stannane in selectivities which surpasses that which is typically afforded under palladium catalysis. Additionally, a telescoped hydrometallation/ cross-coupling sequence has been developed, allowing for application of the vinyl stannanes without excessive manipulation or purification of the intermediate stannane.
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