High-order dipolar annulations with metal-containing reactive dipoles

Abstract

The advances on metal-catalysed high-order dipolar annulations were comprehensively summarized in this review. To further exploit the potential of this unique annulation strategy, a research outlook was also proposed.

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

“…Higher-order cycloaddition involving conjugated systems with more than 6π-electrons, which enables rapid construction of complicated cyclic frameworks, 1 has received considerable attention since its discovery in the 1960s. 2 In spite of its charm in organic synthesis, higher-order cycloaddition generally suffers from low reactivity, and poor periselectivity and stereoselectivity; thus a variety of pre-prepared cyclic polyenes (>4π) have been commonly utilised, including fulvenes, 3 Cr(0)-cycloheptatriene complexes, 4 tropone and its analogues, 5 and 3 H -pyrrolizines, 6 as well as amino-stabilised isobenzofulvenes, 7 in combination with diverse 2π- or 4π-systems under different conditions ( Scheme 1a ).…”

Stereoselective synthesis of C3-tetrasubstituted oxindoles via copper catalyzed asymmetric propargylation

“…Recently, asymmetric propargylation reactions of readily available racemic terminal propargylic esters catalyzed by non-precious chiral copper complexes have emerged as a promising, fruitful and attractive method to construct useful chiral propargyl compounds. 4 However, although a variety of nucleophiles can participate in copper catalyzed propargylation substitution, 5 the efficient construction of contiguous tertiary and all-carbon quaternary stereocenters is still a difficult problem for this methodology. 6 In 2020, Hu and co-workers reported a copper catalyzed asymmetric propargylation reaction of 3-aryl substituted oxindoles affording 3,3-disubstituted oxindoles in highly diastereo- and enantioselective results.…”

C-3 Functionalization of 2-Aryl-2H-indazoles under Photo/Electrocatalysis

“…The past two decades have witnessed the growth of the synthesis of functionalized heterocycles. [7][8][9][10][11][12][13][14][15][16][17] Particularly, a lot of novel methods to construct the 2H-indazole derivatives were developed through direct C-H functionalization. In 2020, Hajra's group [18] reviewed the direct derivation of indazoles.…”