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. 2025 Jul 10;16(1):6349.
doi: 10.1038/s41467-025-61062-z.

A zinc boryl compound unlocks diverse reactivity pathways beyond nucleophilic borylation

Gan Xu #  1 , Hok Tsun Chan #  2 , Shuchang Li  1 , Tsz Ying Wong  1 , Lei Zhang  3 , Qichun Zhang  3 , Zhenyang Lin  4 , Zhenpin Lu  5
Affiliations

A zinc boryl compound unlocks diverse reactivity pathways beyond nucleophilic borylation

Gan Xu et al. Nat Commun. .

Abstract

Borylation chemistry plays a crucial role in the development of new synthetic methodologies. However, the reactivity of zinc-boryl species has not been fully explored, particularly in relation to diverse reaction pathways. Here we show that a zinc-boryl species is successfully synthesized from bis(catecholato)diboron, exhibiting amphiphilic reactivity. This compound acts as a nucleophilic boron anion with methyl iodide and as an electrophile with N,N'-dicyclohexylcarbodiimide, facilitating zinc-boron bond dissociation and generating zinc-carbon and zinc-nitrogen bonds while cleaving carbon-nitrogen double bonds. The enhanced reactivity is likely due to the stronger covalency of the zinc-boron bond. Additionally, the zinc-boryl compound promotes the catalytic diborylation of azobenzene, underscoring its versatility as a reactive intermediate. Density functional theory studies illuminate the electronic structure and reactivity of the zinc-boron bond, providing insights into potential applications in synthetic chemistry.

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Conflict of interest statement

Competing interests: The authors declare the following competing interest(s): A patent application has been filed (applicant: City University of Hong Kong; name of inventor(s): Z. Lu, G.X.; application number 63/728, 912; specific aspect of manuscript covered in patent application, Multi-Functional Zinc-Boryl Reagent for Efficient Synthesis and Catalysis). The remaining authors declare no competing interests.

Figures

Fig. 1
Fig. 1. Examples of Zinc-boryl compounds.
a reported examples of zinc-boryl compounds; b zinc-bornic ester compounds; c zinc-boryl compound reported in this work.
Fig. 2
Fig. 2. Synthesis and structure of compound 1.
a Synthesis of Zinc-boryl compound 1; b Molecular structure of the dimer of compound 1. (thermal ellipsoids are set at the 30% probability level, hydrogen atoms are omitted and the side Dipp parts are set as sticks model for clarity).
Fig. 3
Fig. 3. Electronic structure of compound 1 and a reported Mg(II)-boryl species.
The natural localized molecular orbital (NLMO) plots showing the orbital characters related to the metal-B sigma bonds for 1 (left) and the closely related Mg(II)-boryl species, [HC{(Me)CN(Dipp)}2Mg(DMAP)(Bpin) (right). DFT computation studies were carried out at the BP86 level of theory.
Fig. 4
Fig. 4. Reactivity of compound 1.
a Reaction of compound 1 with DMAP; b Reaction of compound 1 with MeI; c Reaction of compound 1 with N,N’-dicyclohexylcarbodiimide (Molecular structure of compounds 6 and 5: thermal ellipsoids are set at the 30% probability level, hydrogen atoms are omitted and the side Dipp parts are set as sticks model for clarity).
Fig. 5
Fig. 5. Reactivityof compound 1.
a Reaction of compound 1 with isocyanide; b Reaction of compound 1 with azobenzene; c Molecular structure of compound 7. (thermal ellipsoids are set at the 50% probability level, and the hydrogen atoms are omitted for clarity); d Molecular structure of compound 8. (thermal ellipsoids are set at the 30% probability level, hydrogen atoms are omitted and the side Dipp parts are set as sticks model for clarity).
Fig. 6
Fig. 6. Catalytic diborylation of azoarene enabled by compound 1.
The reaction conditions and substrate scope are outlined.
Fig. 7
Fig. 7. Calculated free energy profile for the reaction of compound 1’ with DCC.
Relative Gibbs free energies and relative electronic energies (in parenthesis) are given in kcal/mol. DFT computations were conducted on the reaction of compound 1 with DCC shown in at B97X-D level in toluene.
See this image and copyright information in PMC

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