The total synthesis of oxazolidinone-based pharmaceuticals, linezolid, tedizolid and rivaroxaban is reported. They are synthesized using a recently reported copper-catalyzed one-pot cyclization and arylation as the key step to construct the N-aryloxazolidinone core. Active pharmaceutical ingredients (API) were synthesized from a common synthetic pool of a simple protected amino alcohol in 22 %, 61 % and 40 % total synthesis yields, respectively.

A practical ruthenium-catalyzed O- to S-alkyl migration affords structurally diverse thiooxazolidinones in excellent yields. Our studies suggest this catalytic transformation proceeds through a pseudoreversible radical pathway drawing mechanistic parallels to the classic Barton–McCombie reaction.

A practical ruthenium-catalyzed O- to S-alkyl migration affords structurally diverse thiooxazolidinones in excellent yields. Our studies suggest this catalytic transformation proceeds through a pseudoreversible radical pathway drawing mechanistic parallels to the classic Barton–McCombie reaction.

Several β-arylalanine derivatives containing fluorescent groups were prepared in good yields using a rhodium-catalysed conjugate addition of arylboronic acids to N,N-diprotected and N-monoprotected dehydroalanines. The best conditions for these reactions required the use of an excess of arylboronic acid (4 equiv.), [Rh(COD)₂]BF₄ as catalyst, and CsF as base in dioxane/H₂O (10:1) at 110 °C. These conditions were also applied to several dipeptides with dehydroalanine residues. The photophysical properties of some of the β-arylalanines were studied in three solvents with different polarities. Due to the absence of the α,β-double bond, the absorption and fluorescence emission of the new compounds are dominated by the photophysical properties of the polycyclic aromatic fluorophores (naphthalene, phenanthrene, and pyrene). Considering the relatively high fluorescence quantum yield of these compounds, some of them may be useful as fluorescent markers for peptides and proteins.

The rhodium-catalyzed conjugate addition of organoboron reagents to alkene acceptors has emerged as an important methodology in organic synthesis. The process results in the formation of new carbon–carbon bonds, and in principle, can create new stereocenters at both the α and β carbon atoms of the acceptor. Other organometallics are known to participate in the key transmetalation to rhodium and are becoming more established in stereoselective synthesis (notably arylzinc reagents). This Focus Review will describe recent developments in the use of alternative organometallic donors to organoboron reagents in rhodium-catalyzed conjugate addition reactions and their growing applications in synthesis.