Diacyl peroxides serve as dual-function oxidants and acyloxy sources in a Pd-catalyzed oxidative borylation–acyloxylation of enallenes. Under mild conditions, this protocol delivers stereodefined vinylboronate esters with high chemo- and stereoselectivity across 80+ examples of enallenes and diacyl peroxides. The method avoids external metal or quinone oxidants and is applicable to gram-scale synthesis, product derivatization, and recyclable heterogeneous Pd catalysis. DFT calculations support accessible oxypalladation pathways that converge before C–B bond-forming reductive elimination.

Oxidation reactions are of fundamental importance in nature and often proceed in an enantioselective manner. Palladium-catalyzed oxidative cascade carbocyclizations are efficient protocols for C-C bond formation and cyclic scaffolds construction, thus attracting widespread attention. However, the development of enantioselective versions of these reactions is challenging because commonly used phosphine-based ligands are not tolerated under oxidative conditions. The use of chiral phosphoric acids (CPAs) that provide a chiral counterion to the metal is one solution to this problem. Herein, we report a palladium-catalyzed oxidative enantio-and diastereo-selective carbocyclization-borylation of dienallenes via desymmetrization, enabling the construction of a diverse set of cyclohexenes bearing two nonadjacent stereocenters (up to 99.5:0.5 er and >20:1 dr). The asymmetric induction was obtained by the use of a catalytic amount of chiral diphenyl-3,3'- biphenanthryl-4,4 '-diyl phosphate-phosphoric acid (VAPOL-PA) through significant ligand acceleration. Moreover, the reaction could be advanced into aerobic biomimetic oxidation, where molecular oxygen was used as the terminal oxidant. The introduction of a readily modifiable boronate group with a stereogenic center at the beta-position further demonstrated the synthetic utility of this methodology.

We report a Pd-catalyzed oxidative carbonylative carbocyclization of enallenes that affords 5-methylene cyclopentenones in high yields with excellent regio- and stereoselectivity. The reaction proceeds through olefin-directed allenylic C(sp3)-H activation, and ligand control enables site-selective transformation of unsymmetrical enallenes, favoring the larger alkyl substituent over methyl (up to 20:1). A broad substrate scope and compatibility with heterogeneous Pd-AmP-MCF catalysis and biomimetic aerobic oxidation underscore the practicality and sustainability of the method.

Highly selective conjugate additions of Grignard reagents to cyclic and linear enones catalyzed by recyclable heterogeneous polysaccharide/nanocopper catalysts are disclosed. The method also allows the synthesis of ketones with an all-carbon quaternary center. When integrated with catalytic asymmetric tandem reactions using enals and β-ketoesters, it yields chiral β,δ-disubstituted ketones with high stereoselectivity.

Herein, we present a highly efficient allylic substitution of carbonates with Grignard reagents using a reusable cellulose-supported nanocopper catalyst. This approach highlights the first instance of heterogeneous catalysis for the cross-coupling of allylic alcohol substrates with Grignard reagents. The method features high yields, excellent regioselectivity, and complete chirality transfer.

Direct cross-coupling reactions between two similar unactivated partners are challenging but constitute a powerful strategy for the creation of new carbon-carbon bonds in organic synthesis. [4]Dendralenes are a class of acyclic branched conjugated oligoenes with great synthetic potential for the rapid generation of structural complexity, yet the chemistry of [4]dendralenes remains an unexplored field due to their limited accessibility. Herein, we report a highly selective palladium-catalyzed oxidative cross-coupling of two allenes with the presence of a directing olefin in one of the allenes, enabling the facile synthesis of a broad range of functionalized [4]dendralenes in a convergent modular manner. Specifically, the selective allenic C-H activation of an allene with an allyl substituent as the assisting group gives rise to a vinylpalladium intermediate, which reacts with a less substituted allene in a carbopalladation, followed by a β-hydride elimination. The reaction sequence leads to a new C(sp2)-C(sp2) bond between two diene units. Remarkably, this protocol provides an unconventional strategy for the site-selective and stereoselective construction of C(vinyl)-C(vinyl) bonds without using any halogenated and organometallics olefin precursors. Furthermore, the practical transformations of the synthesized [4]dendralenes and late-stage modifications of biorelevant molecules demonstrate their potential in the total synthesis of natural products and drug discovery.

Nature efficiently produces a myriad of structurally diverse carbon ring frameworks from common linear precursors via cyclization reactions at specific olefinic sites in dienes or polyenes. In contrast, achieving the site-selective functionalization of diene or polyene substrates remains a formidable challenge in chemical synthesis. Herein, we report a pair of highly site-selective, regiodivergent carbocyclization reactions of dienallenes and trienallenes, enabling the efficient synthesis of cis-1,4-disubstituted cyclohexenes and trans-1,2-disubstituted cyclobutenes from a common precursor with high diastereoselectivity. Remarkably, simple achiral organophosphoric acids and amines are identified as powerful ligands for controlling these palladium-catalyzed regiodivergent carbocyclizations. This approach represents the first example of site-selective regiodivergent carbocyclization, providing a practical method for the stereospecific synthesis of thermodynamically disfavored cis-1,4-disubstituted cyclohexenes and fully substituted trans-1,2-cyclobutenes. Additionally, the methodology developed offers general insights into the development of metal-catalyzed site-selective, regiodivergent carbocyclizations of diene and polyene precursors, mimicking natural carbocyclization processes.

Chemoenzymatic dynamic kinetic resolution (DKR), combining a metal racemization catalyst with an enzyme, has emerged as an elegant solution to transform racemic substrates into enantiopure products, while compatibility of dual catalysis is the key issue. Conventional solutions have utilized presynthesized metal complexes with a fixed and bulky ligand to protect the metal from the enzyme system; however, this has been generally limited to anionic ligands. Herein, we report our strategy to solve the compatibility issue by employing a reliable ligand that firmly coordinates in situ to the metal. Such a reliable ligand offers π* orbitals, allowing additional metal-to-ligand d−π* back-donation, which can significantly enhance coordination effects between the ligand and metal. Therefore, we developed an efficient DKR method to access chiral BINOLs from racemic derivatives under dual copper and enzyme catalysis. In cooperation with lipase LPL-311-Celite, the DKR of BINOLs was successfully realized with a copper catalyst via in situ coordination of BCP (L8) to CuCl. A series of functionalized C2- and C1-symmetric chiral biaryls could be synthesized in high yields with good enantioselectivity. The racemization mechanism was proposed to involve a radical-anion intermediate, which allows the axial rotation with a dramatic decrease of the rotation barrier.

A highly efficient dehydrogenative carbonylative esterification of allenoic acids using Pd-catalysis was developed, providing a novel approach to synthesizing esterified γ-butyrolactone derivatives with consistently good to excellent results demonstrated across over 50 examples. Additionally, we used a heterogeneous catalyst known as Pd-AmP-MCF and harnessed biomimetic-aerobic-oxidation conditions to facilitate the practical execution of this reaction. Furthermore, our detailed study of γ-butyrolactone products highlighted their potential in synthesizing bioactive compounds.

Here we report an efficient route for synthesizing strigolactones (SLs) and their derivatives. Our method relies on a palladium-catalyzed oxidative carbonylation/carbocyclization/carbonylation/alkoxylation cascade reaction, which involves the formation of three new C–C bonds and a new C–O bond while cleaving one C(sp³)–H bond in a single step. With our versatile synthetic strategy, both naturally occurring and artificial SLs were prepared.