Rapid and stereoselective synthesis of spirocyclic ethers via the intramolecular Piancatelli rearrangement.

Direct and highly diastereoselective synthesis of azaspirocycles by a dysprosium(III) triflate catalyzed aza-Piancatelli rearrangement.

number of elegant approaches to construct azaspirocycles have been developed. The methods differ in the strategy used to address the two main synthetic challenges: construction of the tertiary carbon center bearing the nitrogen atom, and the formation of the spirocyclic ring system. Generally, the synthetic routes rely on a two-step process where the tertiary carbon center and the spirocycle ar...

A stereo-controlled access to functionalized macrolactams via an aza-Claisen rearrangement.

A novel and stereo-controlled method for the preparation of functionalized macrolactams was developed. The process involves stereoselective enol ether formation, followed by an azacyclic ring expansion via an aza-Claisen rearrangement. Herewith, we describe a systematic investigation of an aza-Claisen rearrangement-induced ring expansion of azacycles prepared by appending E/Z-enol ethers to the...

Synthesis of the C9–C25 Subunit of Spirastrellolide B

The synthesis of the C9-C25 subunit of the marine natural product spirastrellolide B is reported. The key synthetic features included the union of the two key fragments 5 and 6 via a Suzuki-Miyaura coupling reaction and a late-stage, one-pot sequential deprotection/cascade Achmatowicz rearrangement-spiroketalization to install the key spirocyclic intermediate present in the C9-C25 fragment of s...

Highly diastereoselective one-pot synthesis of spirocyclic oxindoles through intramolecular Ullmann coupling and Claisen rearrangement.

Stereoselective synthesis and rearrangement-fragmentation of arylidene N-alkoxydiketopiperazines.

A stereoselective synthesis of arylidene N-alkoxydiketopiperazines via oxime-ether formation and intramolecular acylation is described, followed by an acid-catalysed rearrangement-fragmentation to give novel diketopiperazine hemiaminal derivatives with useful bioactivity against certain tumour cell lines.