BACKGROUND Tashiromine 1 is a naturally occurring indolizidine alkaloid. It has been the subject of thirteen successful total syntheses to date. Our own approach centres on the stereoselective construction of the indolizidine core by capture of an electrophilic acyliminium species by a pendant allylsilane. The key cyclisation precursor is constructed using olefin cross-metathesis chemistry, whi...

Treatment of methyl (Z)-2-alken-4-ynoates with the strong Lewis acid tris(pentafluorophenyl) borane, B(C6F5)3, yield substituted zwitterionic pyrylium borate species via an intramolecular 6-endo-dig cyclisation reaction.

The front cover picture is a metaphor of mechanochemistry. A pair robotic arms playing dominoes with the mechanism Ni-catalyzed domino-cyclisation-arylation o-hydroxyarylenaminones, elucidated by experimental and computational investigations in our group. Meanwhile, another set mechanical contraptions working at 30 Hz about to ground domino tiles as they fall obtain isoflavones under mechanoche...

Isonicotinamides carrying N-furanylmethyl, N-pyrrolylalkyl or N-thiophenylmethyl substituents at nitrogen undergo cyclisation induced by an electrophile, giving spirocyclic compounds or doubly spirocyclic compounds in which both the nucleophilic and electrophilic heterocycles are dearomatised.

In the presence of gold(I)-phosphine catalysts, alkenyl- and arylsilanes undergo intramolecular cyclisation reactions onto appendant alkyne moieties to afford 1-silaindene derivatives. The reaction pathways vary depending on the substituent on silicon.

A short reaction sequence leads to oligoarene derivatives utilising a regioselective Scholl reaction for the unprecedented cyclisation to the mono-functionalised oligoarene under methanol elimination. Quantum-chemical investigations reveal the reason for the remarkably high regioselectivity.

We describe a concise synthesis of (+)-isoaltholactone via a Au-catalysed cyclisation of a monoallylic diol to form the tetrahydrofuranyl ring. Analogous cyclisations show that the stereochemical outcome is dictated by the stereochemistry of the diol substrate.

An unprecedented domino radical cyclisation-Smiles rearrangement process affording 3-(2'-aryl-N-methyl acetamido)indolin-2-ones is presented. Experimental rationalisation of this approach and description of an unexpected tricyclic core are also handled.

A connective Pummerer-type cyclisation involving a cysteine derivative and an N-benzyl glyoxamide 3 has been applied in an asymmetric synthesis of the protected ABH rings 2 of the antitumour and antimicrobial natural product ecteinascidin 597.