Introduction to Vinyl Epoxides

Herein we disclose the first example of the formal hydroacylation reactions of vinyl epoxides with chelating aldehydes enabled by rhodium catalysis for the efficient construction of functionalized esters.

These new dipolarophiles can participate in Pd‐catalyzed asymmetric [3+2] and [4+2] cycloadditions through Pd‐π‐allyl 1,3‐ and 1,4‐zwitterions in‐situ generated by the reaction of Pd(0) catalyst with vinyl aziridines, vinyl epoxides, vinyl cyclopropanes, 4‐vinyl‐1,3‐dioxan‐2‐ones, and vinyl benzoxazinanones.

The first catalytic asymmetric multiple vinylogous addition reactions initiated by Meinwald rearrangement of vinyl epoxides were realized by employing chiral N,N'-dioxide/Sc(III) complex catalysts.

Here, we report the discovery of such a phenomenon in nickel/copper-co-catalyzed divergent allylic alkylation of vinyl epoxides and aziridines using alkynes.

We present an efficient strategy for the formal 1,4-reduction of vinyl epoxides that does not require superstoichiometric amounts of a strong reductant.

A highly efficient Pd-catalyzed asymmetric formal [3+2] cycloaddition using α-N-heterocyclic acrylates to react with vinyl epoxides has been achieved for the first time to access chiral functionalized tetrahydrofuran skeletons (34 examples, up to 93% yield, >20 : 1 dr and 99% ee).

Vinyl epoxides and styrene oxide can react with diborylmethide lithium salts through an exclusive SN 2 borylmethylation/ring opening in a regio- and diastereoselective way, depending on the nature of the substrate.