A new strategy for the one-pot synthesis of polysubstituted benzenes through a N,N-dimethyl-4-aminopyridine (DMAP)-catalyzed [4+2] benzannulation from readily prepared 1,3-bis(sulfonyl)butadienes and γ-substituted allenoates is described. This method provides a facile, metal-free and general route to highly substituted benzenes under mild conditions in moderate-to-good yields with complete regioselectivity.

A strategy was developed to construct dihydropyran and multifunctional cyclopentene derivatives from the same starting materials by using different phosphine catalysts. By exploiting the different nucleophilicities of the phosphine catalysts, the γ-substituted allenoates selectively acted as C₃ or C₂ synthons. Under the catalysis of different organophosphine catalysts, the domino reaction proceeded smoothly with broad substrate tolerance and excellent total yields. The results suggest that the ethyl group of the γ-substituted allenoates played a key role in the domino reaction.

The highly enantioselective intermolecular cross Rauhut–Currier reaction of different active olefins catalyzed by a multifunctional chiral Lewis base was reported. The RC products were obtained in excellent yields (up to 98 %), high chemo- and enantioselectivity (up to 96 % ee). The reaction could be performed on a gram scale using 1 mol % of the multifunctional phosphine catalyst.

The highly enantioselective intermolecular cross Rauhut–Currier reaction of different active olefins catalyzed by a multifunctional chiral Lewis base was reported. The RC products were obtained in excellent yields (up to 98 %), high chemo- and enantioselectivity (up to 96 % ee). The reaction could be performed on a gram scale using 1 mol % of the multifunctional phosphine catalyst.

Sequential catalysis of a [2+4] reaction between a Baylis–Hillman carbonate and a β,γ-unsaturated α-oxo ester for the synthesis of 2-methyl-2H-pyran was developed. The use of a Morita–Baylis–Hillman carbonate as a C₂ synthon is first disclosed in this reaction. This method offers a new approach to the construction of 2-methyl-2H-pyrans and 2-oxabicyclo[2.2.2]oct-5-ene skeletons.

An efficient synthetic approach has been developed for the construction of the spirocyclopentanone skeleton via a phosphine-catalyzed [3+2] annulation reaction. With this novel and economical protocol, various quaternary carbon-centered spirocyclopentanones could be readily obtained.

A novel strategy that involves phosphine-catalyzed sequential [2+3] and [3+2] annulation reactions was developed. In this domino reaction, γ-substituted allenoates were used as novel C₄ synthons, and the bicyclic cyclopenta[b]dihydrofuran derivatives were produced in good to excellent diastereoselectivities and yields under mild conditions. Furthermore, preliminary studies on an asymmetric variant of this reaction proceeded with moderate enantioselectivity.

We have developed a novel strategy to control the product distribution between 2,3-dihydrofurans and biaryls from the same starting materials by tuning the catalytic or stoichiometric process. By controlling the loading of the phosphine PR₃, the Morita–Baylis–Hillman carbonates can be selectively used as a C₁ or a C₃ synthon, respectively. This investigation has given new insights into tunable domino reactions and will be useful in diversity-oriented synthesis (DOS).

The Rauhut–Currier reaction has proved itself as a promising strategy for synthesis of multifunctionalized molecules, although still being in its infancy with regard to limitations of selectivity and scope. Considerable attention has thus been devoted to resolution of difficulties associated with controlling strategies and enantioselectivity. Carbocycles with distinct structural frameworks can be assembled rapidly through incorporation of cross-Rauhut–Currier reactions into domino processes. The fine compatibility and widespread utility of Rauhut–Currier reactions is illustrated with several recent outstanding examples, with the aim of shedding light on the design of new substrates and catalysts for syntheses of complex molecules.

A new tunable phosphine-catalyzed aza-Michael β-addition reaction between allenoates and various hydrazones has been developed. These reactions are most-efficiently promoted by a catalytic amount of phosphine catalysts. These atom-economical reactions are operationally simple and their corresponding adducts can been achieved in high yields and high selectivity under mild reaction conditions. Further studies revealed that different phosphine catalyst can produce different adducts from the same starting materials.