Hydrocarbons are the most abundant organic resource in the planet. The prevalent presence of inert C-H and C-C bonds and relative paucity of functionalities pose unusual constraints in the direct transformation of alkanes and arenes into more valuable chiral functional substances. Thus, the direct asymmetric catalytic functionalization of alkanes and arenes has been a longstanding challenge, and is undoubtedly the frontier in organic synthesis, organometallic chemistry, and catalysis as well. As such, any of breakthroughs in this field represents a leap forward, and more significantly, will propel the proliferation of transformative technologies for fine chemical industry.
The science research center led by Xiaoming Feng of Sichuan University encompasses research teams of Qi-Lin Zhou and Meng-Chun Ye, both at Nankai University, Liu-Zhu Gong of University of Science and Technology of China, also Xiaohua Liu of Sichuan University. All of these principal investigators are among the leading scientists in asymmetric catalysis. For example, chiral N,N'-dioxide ligands and spirocyclic ligands, respectively invented by Feng and Zhou, have constituted two rich families of privileged chiral catalysts that will be able to address stereochemical control issues in asymmetric functionalization given performing reasonable structure modulation. Gong, Liu, and Ye have demonstrated their expertise in the cooperative and relay catalysis of multiple catalysts, that allow bond-breaking and forming events to occur simultaneously or sequentially and hold great potential to orchestrate chemical bonds and to leverage the stereochemistry in the asymmetric functionalization of hydrocarbons. The close collaborations with theoretical chemists and computer specialists will further support the investigation.
The research themes of the center cover key fields of asymmetric transformation of alkanes and arenes. We will concentrate on investigating asymmetric functionalization of the sp3 C-H bond of alkane, and transformation of sp2 C-H bond and carbon-carbon bonds of arene. To address issues associated with these events, a variety of conceptually new ligands and catalysts, featured by “chiral pocket-like conformation” with tunable rigidity, flexibility and “multifunctional interaction”, will be designed. The chiral pocket of the catalysts would create a confined chiral space for the remote control of stereochemistry and minimization of the product-inhibiting effect to thereby refrain the catalyst from deactivation. The multifunctionality is not only to tune the catalytic activity of the metal, but to provide additional interaction to assist the activation of unfunctionalized chemical bonds, principally stabilizes the transition state and hence underpins the stereochemical control. Moreover, the synergistic catalytic strategy via cooperative or relay multi-catalysis will be adopted to balance the bond-cleavage and new bond-formation, benefiting versatile transformations into optical active alcohols, amines, carbonyl derivatives, and multi-substituted cycles. The DFT calculation, big data mining, and three-dimensional imaging analysis, together with modern analytical techniques, will be deployed to understand reaction mechanism and the nature of stereochemical control.
A variety of privileged chiral catalysts that potentially exert great impact on the synthetic community and are broadly amenable to asymmetric catalysis will be invented. Generally inspiring models for controlling stereochemistry in the asymmetric functionalization of hydrocarbons will be established. Some conceptually new and widely useful asymmetric reactions will be established. A number of transformative asymmetric synthetic methods applicable for the industrial production of chiral drugs and other important fine chemicals, will be accomplished. Ultimately, the research center will be an internationally leading team in some fields of asymmetric catalysis.
