Chiral ligands serve as fundamental tools for asymmetric catalysis. Sadphos ligands feature a highly modular backbone. The N‑aryl ring, phosphine substituents and sulfinamide N‑H site can be independently fine‑tuned. By precisely modulating steric and electronic effects, Sadphos ligands are well‑suited for a variety of challenging palladium‑catalyzed tandem cyclization reactions.

These ligands can exert steric shielding effects via bulky substituents. Meanwhile, the intrinsic sulfinamide N‑H hydrogen‑bond donor on the scaffold mediates non‑covalent interactions. Enabled by these two unique modulation modes, four high‑profile research papers have been published within a short period in 2026, including three Angewandte Chemie International Edition articles and one Advanced Science report.

Title: Palladium‑Catalyzed Asymmetric Synthesis of Methylidene Cyclobutanes via Enantioselective Intramolecular Heck‑Type ReactionsAuthors: Haoting Yu, Bing Xu, Junliang Zhang*, Zhan‑Ming Zhang*

The group of Prof. Junliang Zhang and Prof. Zhan‑Ming Zhang at Fudan University developed a palladium‑catalyzed asymmetric intramolecular Heck‑type reaction employing N‑sulfonylhydrazone carbene precursors. Using X9, a XiangPhos variant from the Sadphos family, the bulky adamantyl‑phosphine moiety of the ligand constructs a tailored chiral pocket. It effectively lowers the energy barrier for the desired migratory insertion while elevating the barrier of cyclopropane side‑reactions, suppressing side pathways and racemization. This approach enables efficient access to 1‑methylene‑2‑aryl cyclobutanes with moderate‑to‑good yields, excellent enantio‑ and chemoselectivity (product / cyclopropane by‑product > 20:1).

The reaction exhibits broad substrate scope and is scalable to gram scale. The exocyclic C=C double bond of products can undergo diverse further functionalizations. Mechanistic investigations reveal that the rate‑determining step shifts depending on the electronic property of aryl bromide substrates: 1,2‑aryl‑to‑carbene migration is rate‑limiting for electron‑rich aryl groups, whereas Pd‑carbene formation becomes rate‑determining for electron‑withdrawing substituents. Non‑linear‑effect experiments confirm that monomeric Pd‑X9 complex represents the catalytically active chiral species. This work offers a practical strategy for asymmetric construction of highly strained chiral cyclobutane skeletons.

Title: Asymmetric Allylic Dearomatization of Quinolines via Dynamic Ligand ExchangeAuthors: Jian‑Feng Xu, Li Zhou, Xue‑Pei Bai, Bing Xu*, Yi‑Xia Jia*, Wen‑Yu Huang*

A collaborative team from Zhejiang University of Technology (Prof. Yi‑Xia Jia, Prof. Wen‑Yu Huang) and Naval Medical University (Dr. Bing Xu) utilized MingPhos from the Sadphos family. Taking full advantage of the sulfinamide N‑H hydrogen‑bond donor on the ligand scaffold and hard‑soft acid‑base theory, pre‑assembly between substrate and ligand is realized through N‑H···O hydrogen‑bonding interaction, which drives dynamic ligand‑exchange processes. Racemic Pd‑species with quinoline coordinated to metal center are reversibly converted into chiral active palladium catalysts. A confined microenvironment is established to govern the stereochemistry of allylic C‑N bond formation.

Thereby, the first Pd/Cu dual‑catalyzed tandem asymmetric allylic dearomatization of quinolines involving terminal alkynes is accomplished. Chiral nitrogen‑heterocyclic products bearing two consecutive stereocenters are assembled in one step, delivering yields up to 85 %, ee values up to 99 % and diastereoselectivity d.r. >20:1. Good functional‑group tolerance is observed. Gram‑scale synthesis and diverse late‑stage derivatization of products are feasible.

In‑situ ³¹P NMR directly visualizes the dynamic ligand‑exchange phenomenon. Control experiments combined with DFT calculations corroborate that the N‑H hydrogen bond within MingPhos is essential for stereoinduction; disruption of hydrogen bonding leads to complete loss of enantioselectivity.

Title: Pd‑Catalyzed Enantioselective Construction of Isoindolo[2,1‑a]indolesAuthors: Genwei Zhang, Velayudham Sankar, Jiahao Chen, Shanshan Li, Junfeng Yang*, Junliang Zhang*

Prof. Junliang Zhang and Prof. Junfeng Yang’s group at Fudan University performed structural iteration on MingPhos (Sadphos family). By installing 3,5‑di‑tert‑butyl substituents on the ligand N‑aryl ring and electron‑rich groups on the phosphine fragment, a stereodifferentiated chiral pocket is built. Pronounced steric repulsion differences among competing transition states enable efficient facial discrimination of the imine C=N double bond and achieve high facial‑selectivity for this key step.

Accordingly, the first palladium‑catalyzed asymmetric Larock‑type cyclization reaction is realized, furnishing a series of chiral isoindolo[2,1‑a]indole derivatives with up to 98 % ee. The reaction can be scaled‑up to gram quantities, and products are amenable to late‑stage Suzuki‑Miyaura modification. Mechanistic studies indicate that monomeric Pd‑M6 complex is the active catalytic species; migratory insertion of alkenyl‑Pd onto C=N constitutes the enantio‑determining step, while C‑H bond activation is rate‑determining.

Moreover, the obtained fused‑ring compounds exhibit high fluorescence quantum yields and distinct circular dichroism signals, extending their application prospect toward chiral circularly‑polarized luminescence optoelectronic materials.

Title: Pd‑Catalyzed Asymmetric Dearomative Heck/Tsuji‑Trost Difunctionalization of NaphthalenesAuthors: Long‑Ling Ma, Bing Xu, Junliang Zhang*, Zhan‑Ming Zhang*

Fudan University’s Junliang Zhang & Zhan‑Ming Zhang research group adopted a bulky MingPhos variant from the Sadphos family. A congested chiral pocket is constructed by steric‑shielding effect of the ligand. It suppresses unproductive amine‑to‑Pd coordination and various competing side pathways. Meanwhile, two remote stereocenters are precisely controlled in two sequential steps: migratory insertion and nucleophilic attack onto π‑allylpalladium intermediate.

Thus palladium‑catalyzed asymmetric dearomative tandem Heck/Tsuji‑Trost 1,4‑difunctionalization of naphthalenes is achieved, efficiently affording chiral 4‑amino spirocyclohexenyl oxindole derivatives. Broad substrate compatibility is demonstrated: alkyl amines, aryl amines and several drug‑derived amines all participate well in this transformation, with maximum ee reaching 97 %. Gram‑scale synthesis is supported. Multiple late‑stage transformations can be performed at product moieties including C=C double bond, amide and secondary amine N‑H. Non‑linear‑effect mechanistic experiments confirm that monomeric Pd‑M4 complex serves as catalytic active species. This work provides new ligand‑design insights for complex tandem dearomatization of non‑activated arenes.

To facilitate related scientific research, Kaitailai Platinum (Anhui) Co., Ltd. stocks more than 200 structurally diverse Sadphos‑family ligands including Ming‑Phos and Xiang‑Phos. Representative products are available off‑the‑shelf. Global inquiries and cooperation are warmly welcomed.