The Modified Sakurai and Related Reactions

Highly Diastereoselective Silyl‐Modified Sakurai Multicomponent Reaction

“…This adduct should contain portions of all the individual components, and at least one new stereogenic center should be generated. [12] For some time, we have been interested in the silylmodified Sakurai reaction (also known as the Sakurai MCR), [13] especially the catalytic and intramolecular version. [14][15][16] The Sakurai MCR involves the Lewis acid catalyzed condensation of carbonyl derivatives (ketones, aldehydes, ketals, hemiketals, orthoesters, ortholactones) with allylic silanes and alcohols (or silyl ethers), thus yielding the corresponding homoallylic ethers (Scheme 1).…”

Brønsted Acid‐Catalyzed Three‐Component Hosomi–Sakurai Reactions

“…However, many acetals are not commercially available and have to be synthesized from the corresponding aldehydes (2). In addition, most of these Hosomi-Sakurai reactions [1] give rise to homoallyl methyl ethers bearing a protecting group that requires harsh conditions to be cleaved.…”

Tandem Reactions Involving 1-Silyl-3-Boryl-2-Alkenes. New Access to (Z)-1-Fluoro-1-Alkenes, Allyl Fluorides, and Diversely α-Substituted Allylboronates

“…Allylboronic esters and allylsilanes have been proven to be highly versatile carbon nucleophiles, usually showing very good levels of chemo-, regio-, and stereocontrol in various reactions with electrophiles. Both of them can add to carbonyl derivatives in the presence, or absence, of a Lewis acid activator . In addition, allylboronic acids can also be engaged in palladium-catalyzed cross-couplings and conjugate allylation of electron-deficient alkynes .…”