Aijun Lin

Switchable Z / E stereocontrol with NaH or H ₂ SO ₄ enables divergent synthesis of multi-substituted 1,3-dienes via sequential allylation/Peterson elimination.

Catalytic asymmetric construction of C─O axially chiral diaryl ethers remains underdeveloped relative to C─C biaryl atropisomers, and examples that simultaneously create a stereogenic carbon center are scarce. Herein, we report a chiral phosphoric acid‐catalyzed enantioselective allyl addition of prochiral dialdehydes with allylboronate, which enables the efficient synthesis of a novel class of axially chiral diaryl ethers bearing both C─O axial chirality and a stereogenic benzylic carbon center. This protocol provides the desired products in good diastereoselectivities and enantioselectivities under mild conditions. The retained aldehyde group serves as a versatile handle for diverse downstream transformations, substantially enhancing the structural and functional diversity of the atropisomeric scaffolds.

Double-allylation reagents serve as powerful linchpins for assembling two electrophiles, such as aldehydes. Although great advances have been made in the construction of achiral double-allylation reagents, the catalytic enantioselective synthesis and application of linear 1,3-bifunctional allylborons remain rarely developed. Herein, we report a copper-catalyzed enantio-, regio-, and E/Z-selective hydroboration of 1,3-dienylsilanes to afford bifunctional allylation reagents bearing a chiral center at the allylic position. The kinetic resolution process of the E/Z-mixture of dienylsilanes ensures high ee of products regardless of the initial E/Z-ratio. Density functional theory (DFT) studies were conducted to probe the origins of the enantio- and E/Z-selectivities. Sequential allylation of aldehydes with the newly developed double-allylation reagents can construct chiral 3,6-dihydropyrans and pent-2-ene-1,5-diols bearing four contiguous stereocenters with excellent diastereoselectivities and enantioselectivities.

We report an efficient, metal-free protocol for the direct synthesis of ketones from carboxylic acids and (hetero)arylboronic acids, proceeding via a 1,3-boronate shift of a tetracoordinate boron species.

The enantioselective synthesis of novel atropisomeric architectures represents a key driving force in the advancement of functional materials, drug discovery, and asymmetric catalysis. While great progress has been made in the enantioselective synthesis of biaryl atropisomers, the catalytic enantioselective synthesis of atropisomeric acyclic 1,3‐dienes is still elusive due to the inherently low rotational barrier of the C‐C bonds. Herein, we report a platinum‐catalyzed enantioselective hydrosilylation of enynes. Using a monophosphine ligand L1 , the atropisomeric 1,3‐dienes are constructed in good yield with enantioselectivity and excellent regio‐ and E ‐selectivity. Density functional theory (DFT) calculations are conducted to elucidate the origin of the regio‐ and enantioselectivity. Crucially, the basic additive such as KOH and K ₃ PO ₄ works as a proton shuttle to promote the reaction.

The enantioselective synthesis of novel atropisomeric architectures represents a key driving force in the advancement of functional materials, drug discovery, and asymmetric catalysis. While great progress has been made in the enantioselective synthesis of biaryl atropisomers, the catalytic enantioselective synthesis of atropisomeric acyclic 1,3‐dienes is still elusive due to the inherently low rotational barrier of the C‐C bonds. Herein, we report a platinum‐catalyzed enantioselective hydrosilylation of enynes. Using a monophosphine ligand L1 , the atropisomeric 1,3‐dienes are constructed in good yield with enantioselectivity and excellent regio‐ and E ‐selectivity. Density functional theory (DFT) calculations are conducted to elucidate the origin of the regio‐ and enantioselectivity. Crucially, the basic additive such as KOH and K ₃ PO ₄ works as a proton shuttle to promote the reaction.

While bifunctional allylation reagents have proven effective for constructing complex molecules bearing multiple central chirality, their potential for assembling axially chiral scaffolds remains undeveloped. Herein, we report a BINOL-catalyzed enantioselective allylation of prochiral carbonyl compounds using a type I bifunctional allylation reagent, which affords enantioenriched β-hydroxy silanes. The central chirality of these adducts is then efficiently transferred to axially chiral alkylidenecycloalkanes via an acid/base-controlled, enantiodivergent Peterson elimination. Moreover, this strategy is successfully extended to the enantioselective assembly of axially chiral diaryl ethers with three contiguous chiral elements. The dienyl motifs of the axial products provide a platform for further transformations. Density functional theory calculations are performed to elucidate the origin of the enantioselectivity.

A copper-catalyzed three-component radical relay alkenylation of sulfenamides was developed, providing β-trifluoromethyl alkenyl sulfilimines in good yields with excellent stereoselectivity.

A copper-catalyzed enantioselective interrupted azide–alkyne cycloaddition was developed, enabling the facile construction of axially chiral diaryl ethers bearing a 1,4,5-trisubstituted triazole moiety directly from terminal alkynes.

A palladium-catalyzed sequential hydroarylation and hydroalkylation of 1,3-enynes was developed, providing efficient access to cyclopenta[ b ]indoles and their derivatives in good yields with excellent chemoselectivities.