The synthesis of a second-generation [6]-helicenoidal DMAP organocatalyst is reported. The synthesis is reliant upon a highly diastereoselective Rh-catalysed [2 + 2 + 2] triyne cycloisomerization, using an existing stereocentre to control the sense of forming helicity. Taken together, a scalable (>1 g), resolution-free entry to a helical DMAP with the capacity for subsequent functionalization, has been achieved.
The oxidation of alkyl and aryl aldehydes to their corresponding carboxylic acids has been achieved through the action of a biomimetic bridged flavin catalyst. The reaction uses readily available 35% aqueous hydrogen peroxide and is operationally simple. The oxidation is a green and sustainable reaction, obviating chlorinated solvents with minimal byproducts.
The Ireland-Claisen [3,3]-sigmatropic rearrangement has been used to access biologically important β,β'-dihydroxy α-amino acids. The rearrangement reported is highly stereoselective and offers excellent levels of remote stereocontrol. This strategy has been used to synthesize the natural immunosuppressant mycestericin G and ent-mycestericin G, allowing for a revision of absolute configuration of this natural product.
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