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Page 8 of 10 Xu et al. Chem Synth 2023;3:17 https://dx.doi.org/10.20517/cs.2022.35

Figure 2. The calculated free energy profile and geometries of the key transition states for the enantioselectivity-determining Michael
addition step (calculations were performed at the M06/6-311++G(d,p)/SDD//B3LYP-D3BJ/6-31G(d,p)/LANL2DZ//
SMD(solvent=Acetonitrile) level of theory; bond distances are given in Å).

CONCLUSION
In conclusion, we have disclosed a novel acyl transfer-enabled catalytic asymmetric Michael reaction of α-
hydroxy-1-indanones with nitroolefins via an underexplored electrophilic mode of activation. The chemical
event underwent a reaction cascade of dinuclear zinc-catalyzed asymmetric Michael addition,
intramolecular cyclization, and the retro-Claisen reaction. Good yields and stereoselectivities of the desired
products were obtained with a wide substrate scope under mild conditions. In the activation mode, the
dinuclear zinc complex acted as a bifunctional catalyst, wherein one zinc atom worked as a Lewis acid and
the another functioned as a Brønsted base. Further applications of this catalytic asymmetric acyl transfer via
electrophile activation for the synthesis of polyfunctional heterocycles are ongoing in our laboratory.

DECLARATIONS
Authors’ contributions
Designing the experiments, writing the manuscript, and being responsible for the whole work: Jia SK, Wang
MC, Mei GJ
Performing the experiments: Xu ZH, Hua YZ
Synthesizing the substrates: Chang ZR
DFT calculations: Li N, Xu LP

Availability of data and materials
Supplementary materials are available online for this paper.

Financial support and sponsorship
Financial support from the Natural Science Foundation of Henan Province (222300420084, 222300420292),
China Postdoctoral Science Foundation (2022M712862), application research plan of Key Scientific
Research Projects in Colleges and Universities of Henan Province (22A150056), and Zhengzhou University