Asymmetric higher-order [10 + n] cycloadditions of palladium-containing 10π-cycloaddends

Abstract

We uncovered an asymmetric higher-order [10+2] cycloaddition reaction between diverse activated alkenes and a new type of π-allylpalladium complex-containing dipole-type 10π-cycloaddends, which were generated in situ from 2-methylene-1-indanols via a...

Palladium‐Catalyzed [4 + 4] Cycloaddition of Homo‐TMM All‐Carbon 1,4‐Dipole Precursors for Construction of Benzofuro[3,2‐b]azocines and Furo[3,2‐b]azocines

“…[ 9 ] To date, an assortment of TMM dipole precursors has been developed to enable the efficient construction of cyclic compounds (Scheme 1a), encompassing methylene cyclopropanes, [ 10 ] 2‐substituted allyl carbonates (Trost‐TMM), [ 9h,11‐12 ] γ ‐methylidene‐ δ ‐valerolactones, [ 8g,13 ] 2‐methylidenetrimethylene carbonates, [ 14 ] pyrrolidines, [ 15 ] 2‐methylene‐ 1‐indanols. [ 16 ] Among various types of TMM dipole precursors, Trost‐TMM is the most extensively investigated one, which served as an efficient three‐carbon unit in Pd‐catalyzed [3 + n ] cycloadditions. [9h] In this field, our group successfully realized several asymmetric [3 + 4] cycloadditions of Trost‐TMM precursors with different 4‐atom synthons, furnishing a series of fused azepines or cycloheptanes with excellent regio‐, diastereo‐ and enantioselectivities in recent years (Scheme 1b).…”

Palladium-catalyzed [4 + 4] cycloaddition of homo-TMM all-carbon 1,4-dipole precursors for the construction of benzofu-ro[3,2-b]azocines

“…[9] To date, an assortment of TMM dipole precursors has been developed to enable the efficient construction of cyclic compounds (Scheme 1a), encompassing methylene cyclopropanes, [10] 2-substituted allyl carbonates (Trost-TMM), [9h,11,12] γ -methylideneδ -valerolactones, [8g,13] 2-methylidenetrimethylene carbonates, [14] pyrrolidines, [15] 2-methylene-1-indanols. [16] Among various types of TMM dipole precursors, Trost-TMM is the most extensively investigated one, which served as an efficient three-carbon unit in cycloadditions. [9h] In this field, our group successfully realized several asymmetric [3 + 4] cycloadditions of Trost-TMM precursors with different 4atom synthons, furnishing a series of fused azepines or cycloheptanes with excellent regio-, diastereo-and enantioselectivities in recent years (Scheme 1b).…”