Correction: Asymmetric catalytic [1,3]- or [3,3]-sigmatropic rearrangement of 3-allyloxy-4-chromenones and their analogues.

[This corrects the article DOI: 10.1039/D4SC02201G.].

Asymmetric catalytic [1,3]- or [3,3]-sigmatropic rearrangement of 3-allyloxy-4-chromenones and their analogues.

A highly efficient asymmetric [1,3]- and [3,3]-O-to-C sigmatropic rearrangement of 3-allyloxy-4-chromenones and their analogues was developed. Chiral ,'-dioxide complexes of 3d late transition metal complexes enabled two mechanistically different processes, giving a series of optically active 2,2-disubstituted chromane-3,4-diones and 2-allyl-3-hydroxy-4-chromen-4-ones as well as their related compounds in excellent yield and enantioselectivity. Systemic mechanistic studies and DFT calculation revealed the nature of the vinyl ether unit of the substrate, which biased regioselectivity a stepwise tight ion pair pathway and a concerted pericyclic pathway, respectively.

Asymmetric synthesis of complex tricyclo[3.2.2.0]nonenes from racemic norcaradienes: kinetic resolution Diels-Alder reaction.

Herein, the enantioselective synthesis of complex tricyclo[3.2.2.

Recent advances in metal-catalysed asymmetric sigmatropic rearrangements.

Asymmetric sigmatropic rearrangement is a powerful organic transformation substrate-reorganization to efficiently increase molecular complexity from readily accessible starting materials. In particular, a high level of diastereo- and enantioselectivity can be readily accessed through well-defined and predictable transition states in [3,3], [2,3]-sigmatropic rearrangements, which have been widely applied in the synthesis of various chiral building blocks, natural products, and pharmaceuticals. In recent years, catalytic asymmetric sigmatropic rearrangements involving chiral metal complexes to induce stereocontrol have been intensively studied.

Asymmetric synthesis of chromanone lactones vinylogous conjugate addition of butenolide to 2-ester chromones.

Chiral chromanone lactones are a class of natural products with important biological activity. We report a direct diastereo- and enantioselective vinylogous conjugate addition of butenolide to 2-ester substituted chromones. The transformation proceeded well in the presence of as low as 1 mol% of a chiral ,'-dioxide/Sc complex, 3 Å MS and a catalytic amount of hexafluoroisopropanol (HFIP).

Enantioselective [1,2]-Stevens rearrangement of thiosulfonates to construct dithio-substituted quaternary carbon centers.

An enantioselective [1,2] Stevens rearrangement was realized by using chiral guanidine and copper(i) complexes. Bis-sulfuration of α-diazocarbonyl compounds was developed through using thiosulfonates as the sulfenylating agent. It was undoubtedly an atom-economic process providing an efficient route to access novel chiral dithioketal derivatives, affording the corresponding products in good yields (up to 90% yield) and enantioselectivities (up to 96 : 4 er).

Asymmetric synthesis of isochromanone derivatives trapping carboxylic oxonium ylides and aldol cascade.

An efficient asymmetric synthesis of isochromanone derivatives was realized through -selective-1,3-OH insertion/aldol cyclization reaction involving acyclic carboxylic oxonium ylides. The combination of achiral dirhodium salts and chiral ,'-dioxide-metal complexes, along with the use of α-diazoketones instead of α-diazoesters, enables the cascade reaction efficiently. A variety of benzo-fused δ-lactones bearing vicinal quaternary stereocenters were obtained with good to excellent enantioselectivity, bypassing the competitive 1,1-OH insertion and racemic background aldol reaction.

Chiral Fe(ii) complex catalyzed enantioselective [1,3] O-to-C rearrangement of alkyl vinyl ethers and synthesis of chromanols and beyond.

A highly efficient enantioselective [1,3] O-to-C rearrangement of racemic vinyl ethers that operates under mild conditions was developed. This method with chiral ferrous complex catalyst provided an efficient access to a wide range of chromanols with high yields and excellent enantioselectivities. In addition, an important urological drug ()-tolterodine and others were easily obtained after simple transformations.

A chiral cobalt(ii) complex catalyzed enantioselective aza-Piancatelli rearrangement/Diels-Alder cascade reaction.

A chiral ,'-dioxide/cobalt(ii) complex catalyzed highly diastereoselective and enantioselective tandem aza-Piancatelli rearrangement/intramolecular Diels-Alder reaction has been disclosed. Various valuable hexahydro-2,5-epoxycyclopenta[]isoindoles bearing six contiguous stereocenters have been obtained in good yields with excellent diastereo- and enantio-selectivities from a wide range of both readily available 2-furylcarbinols and -(furan-2-ylmethyl)anilines.

Chiral ,'-dioxide/Mg(OTf) complex-catalyzed asymmetric [2,3]-rearrangement of generated ammonium salts.

Catalytic enantioselective [2,3]-rearrangements of generated ammonium ylides from glycine pyrazoleamides and allyl bromides were achieved by employing a chiral ,'-dioxide/Mg complex as the catalyst. This protocol provided a facile and efficient synthesis route to a series of -α-amino acid derivatives in good yields with high stereoselectivities. Moreover, a possible catalytic cycle was proposed to illustrate the reaction process and the origin of stereoselectivity.