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Award ID contains: 2018501

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  1. Abstract In contrast to phosphine oxides and arsine oxides, which are common and exist as stable monomeric species featuring the corresponding pnictoryl functional group (Pn=O/Pn+–O; Pn = P, As), stibine oxides are generally polymeric, and the properties of the unperturbed stiboryl group (Sb=O/Sb+–O) remain unexplored. We now report the isolation of the monomeric stibine oxide, Dipp3SbO (where Dipp = 2,6-diisopropylphenyl). Spectroscopic, crystallographic and computational studies provide insight into the nature of the Sb=O/Sb+–Obond. Moreover, isolation of Dipp3SbO allows the chemistry of the stiboryl group to be explored. Here we show that Dipp3SbO can act as a Brønsted base, a hydrogen-bond acceptor and a transition-metal ligand, in addition engaging in 1,2-addition, O-for-F2exchange and O-atom transfer. In all cases, the reactivity of Dipp3SbO differed from that of the lighter congeners Dipp3AsO and Dipp3PO. 
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  2. Abstract We report the first total synthesis of an antimycobacterial natural product oxazinin A that takes advantage of a multi‐component cascade reaction of anthranilic acid and a precursor polyketide containing an aldehyde. The route utilized for the synthesis of the pseudodimeric oxazinin A validates a previously proposed biosynthetic mechanism, invoking a non‐enzymatic pathway to the complex molecule. We found a 76 : 10 : 9 : 5 ratio of oxazinin diastereomers from the synthetic cascade, which is an identical match to that found in the fermentation media from the fungusEurotiomycetes110162. Further investigation of the non‐enzymatic formation of oxazinin A using1H‐15N HMBC NMR spectroscopy allowed for a plausible determination of the stepwise mechanism. The developed route is highly amenable for the synthesis of diverse sets of analogs around the oxazinin scaffold to study structure–activity relationships (SAR). 
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  3. Free, publicly-accessible full text available January 13, 2026
  4. We synthesize and characterize As(Cys)3, Sb(Cys)3, and Bi(Cys)3, describe their crystal structures, analyze structural trends across Pn(SR)3compounds, and compare their features to the structures of proteins with these centers bound to Cys3motifs. 
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    Free, publicly-accessible full text available December 3, 2025
  5. Free, publicly-accessible full text available October 2, 2025
  6. The synthetic strategies employed to isolate monomeric stibinidene chalcogenides (RSbCh) and monomeric stibine chalcogenides (R3SbCh) are discussed, and a perspective on the outcomes and future directions of this exciting area is provided. 
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    Free, publicly-accessible full text available May 21, 2025