Recent advances in Pd-catalyzed asymmetric cyclization reactions

Abstract

This review aims to collect advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years, and it is organized into thirteen sections depending on the different types of transformations involved.

Advances in the synthesis of rearranged homoisoflavonoids

“…These enantioselective versions hold great promise for the future availability of these compounds in biological assessments. 110–115 Additionally, this work revisited the synthesis of two other skeletons: protosappanin-type and scillascillin-type. Interestingly, these skeletons remain relatively unexplored, with only a few reported strategies thus far.…”

Palladium-Catalyzed Ligand-Controlled Switchable Hetero-(5 + 3)/Enantioselective [2σ+2σ] Cycloadditions of Bicyclobutanes with Vinyl Oxiranes

“…Notably, none of these ring expansion methods have a catalytic asymmetric version. As a part of our continual program in the discovery of new reactions of vinyl oxiranes, herein, we present our design for palladium-catalyzed cross-dimerization and hetero-(5+3) cycloadditions strategy of vinyl oxiranes − and BCBs to address the challenges encountered in BCB chemistry. We hypothesized that the selective oxidative addition of a Pd(0) complex to vinyl oxiranes would result in the formation of the palladium intermediate Int-I .…”

Iridium-Catalyzed Asymmetric Hydroarylation of Unactivated Alkenes with Heterobiaryls: Simultaneous Construction of Axial and Central Chirality

“…W ith the expanding importance and quest for enantiopure molecules, asymmetric catalysis has been one of the most rapidly developing fields in organic chemistry. 1 Methodologies for the preparation of molecules bearing a single chiral element have been well developed. The reported methods focus predominantly on the controlling one or two stereogenic centers, 2 with the construction of axial chirality also attracting a special interest (Scheme 1A, left).…”

“…Reaction conditions: 1a (0.50 mmol), 2a (0.20 mmol), [Ir(cod)Cl] 2 (5 mol %), ligand (12 mol %), NaBAr F (12 mol %), 1,4-dioxane (2 mL), 130 °C, 48 h. The ratios of 3a:4a and dr were determined by1 H NMR spectra of the crude product. er was determined via chiral HPLC analysis.…”