Article A: J. Am. Chem. Soc. 2021, 143, 12445-12449. ((until 2024 citations>10)

Key research results:

While BINOL and SPINOL, together with their derivatives (e.g., chiral phosphoric acids and chiral phosphoramides) have been widely known as chiral catalysts and ligands for asymmetric catalysis, their performance varied based on different reactions and often complements each other. In 2021, Prof. Jianwei Sun's research team at the Hong Kong University of Science and Technology reported a new chiral skeleton, SPHENOL, which combines the advantages of BINOL and SPINOL. This unique property makes the SPHENOL skeleton a new platform for the development of chiral ligands and catalysts. Its superior performance has been demonstrated in different reactions, and these results indicate the great potential of this type of spirocyclic skeleton for modern synthesis.

Some typical applications of SPHENOL-based catalysts and their comparison with the SPINOL and BINOL counterparts are shown below.

1. SPHENOL-derived phosphoramide as a ligand for asymmetric hydrogenation reactions:

2. SPHENOL-derived phosphoramide as a ligand for asymmetric hydroacylation:

3. SPHENOL-derived CPA as catalyst for spirocyclization for the synthesis of SPHENOL:

4. SPHENOL-derived CPA as catalyst for spirocyclization for the synthesis of the SPINOL precursor:

5. SPHENOL-derived CPA as catalyst for asymmetric synthesis of oxazolines:

Article B: J. Am. Chem. Soc. 2025, xxx, XXX-XXX.  (online, DOI : 10.1021/jacs.4c16062)

Article research skeleton:（SPHENOL-derived new CPA）

The reactions of successful application of the structure:

Brief introduction to the research:

In biochemistry, amine derivatives serve as fundamental structural units, boasting a ubiquitous presence and significant importance in medicinal chemistry. With advancements in chemical synthesis techniques, researchers have increasingly focused on preparing carborane derivatives modified by organic nitrogen groups. In this domain, the role of catalysts is particularly pronounced, as they facilitate the efficient synthesis of carborane-amino acid or -nucleotide conjugates, which have shown immense potential as candidates for cancer therapy in boron neutron capture therapy (BNCT). In the study of catalysis and functional materials, amine-containing carboranes and other derivatives have emerged as unique ligands for transition metal complexes and building blocks for functional molecules. However, the three-dimensional σ-aromaticity and electronic induction effects (electron-withdrawing effect of carbon terminal substituents and electron-donating effect of boron terminal substituents) of carborane clusters pose significant challenges for functionalization strategies. In these complex synthetic processes, the selection and optimization of catalysts become the key to solving problems. Despite certain progress made in carborane functionalization in recent years, challenges such as asymmetric synthesis and direct alkylation of 1-amin-o-carborane (1-NH₂-o-C₂B₁₀H₁₁) remain unresolved. To overcome these existing challenges, the novel chiral phosphoric acid derived from SPHENOL developed by our team has played a crucial role.