Simple Alkenes as Substitutes for Organometallic Reagents:  Nickel-Catalyzed, Intermolecular Coupling of Aldehydes, Silyl Triflates, and Alpha Olefins

Abstract

A nickel-catalyzed method for the three-component coupling of alkenes (ethylene and alpha olefins), aldehydes, and silyl triflates is described, and this process represents the first catalytic method for coupling aldehydes and alkenes to give allylic alcohol derivatives. Conceptually, the alkene functions as a replacement for an alkenylmetal reagent.

Transition metals in organic synthesis: Highlights for the year 2005

“…Nickel catalyzed the coupling of mono-substituted alkenes with aldehydes in the presence of TMS-triflate to give allylic TMS-ethers (Eq. (169)) [912]. Rhodium catalyzed a reductive coupling of conjugated alkynes with ethyl (N-sulfinyl)iminoacetates in the presence of hydrogen gas (Eq.…”

Nickel Catalysis: Synergy between Method Development and Total Synthesis

“…These investigations bore their first fruit in 2005, when we disclosed our first example of a nickel-catalyzed alkene–aldehyde coupling (Scheme 13). Closely related to both the carbonyl–ene and Prins reactions, this multi-component reaction couples terminal olefins (including ethylene), aldehydes, and silyl triflates to form silyl-protected allylic 32 or homoallylic alcohols. 33 In contrast to prototypical carbonyl–ene chemistry, less substituted alkenes, such as ethylene and terminal alkenes, are more reactive coupling partners than di-, tri-, and tetrasubstituted alkenes.…”

Transition‐Metal‐Catalyzed Laboratory‐Scale Carbon–Carbon Bond‐Forming Reactions of Ethylene

“…[21] The reaction is generally high yielding under mild reaction conditions, including ambient pressure and temperature. Sterically hindered, non-enolizable aldehydes work best, including those leading to 29a – d , and a wide variety of alkyl silyl triflates are well tolerated.…”