Metal‐Catalyzed Substrate‐Directed Enantioselective Functionalization of Unactivated Alkenes

Abstract

Alkenes are versatile compounds that are available on large scales in industry or through chemical synthesis. Selective functionalization of unactivated alkenes in a chemo‐, regio‐, diastereo‐ and enantioselective fashion is a highly sought‐after goal in organic synthesis. Substrate‐directed enantioselective functionalization of unactivated alkenes provides an important strategy to achieve this goal. Using a functional group on the alkene substrate as a native coordinating group, a two‐point binding mode of the substrate to the metal center enables effective control of regio‐, diastereo‐ and enantioselectivities. Through this strategy, a variety of enantioselective functionalization methods have been developed recently. The recent advances in this area are highlighted here.

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

“…Accordingly, substantial endeavors have been witnessed in developing new synthetic methods to access or utilize this class of compounds. [ 1‐7 ] Among the developed methods, transition metal‐catalyzed difunctionalization of alkenes enables preparation of complex molecules from simple available alkenes by diversifying the C=C double bond with high atom‐ and step‐economic efficiency. [ 8‐21 ] In particular, the dicarbofunctionalization of alkenes has gained special attention because it can construct complex carbon skeletons by assembling two carbon entities across the C=C bond and forming two C—C bonds in an one‐pot reaction (Scheme 1).…”

Enantioselective synthesis of tertiary boronic esters through catalytic asymmetric reversed hydroboration

“…We surmised that a metal-catalyzed reversed hydroboration of β,β-disubstituted α,β-unsaturated amide would provide an entry to address this challenge (Fig. 1c ) 53 – 56 . In this strategy, a hydride is first incorporated at the α position followed by delivery of the boryl group at the β position, which is mechanistically distinct from a boryl conjugate addition (vide infra).…”

Copper-catalyzed radical oxyallylation of olefins for the construction of alkene-containing isoxazolines

“…The direct difunctionalization of alkenes, a valuable and readily available feedstock, represents one of the most effective strategies for increasing molecular complexity in synthetic organic chemistry. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Among them, the oxyallylation of alkenes is a particularly useful reactions, because the alkenes motif in the resulting products offer rich possibilities for synthetic manipulations. Despite significant advances in the oxyfunctionalization of alkenes, [17][18][19][20][21][22][23][24][25][26] oxyallylation of alkenes have been little explored.…”