The Smiles Rearrangement and the Julia–Kocienski Olefination Reaction

Abstract

Molecular rearrangements consisting of base- or acid-induced dislocation of aromatic or heteroaromaticrings are reviewed. The emphasis is given to recent developments and, in particular, to synthetic applicationof the rearrangement. A novel classification has been applied in order to discuss systematically ratherdiverse published data. The rearrangements are reviewed according to atoms entering and leaving the ipso-position of the migrating ring. The Julia-Kocienski olefination reactionis presented in other parts of this volume.

Arylsulfonylacetamides as bifunctional reagents for alkene aminoarylation

“…To contrast the widely investigated field of transition metal-mediated aminoarylation and build on the successes of photocatalytic alkene difunctionalization chemistry, we were inspired by the possibility of a radical Smiles-Truce rearrangement to provide alkene aminoarylation products in a diastereoselective fashion. Traditionally, the Truce variant of the Smiles rearrangement is a nucleophilic aromatic substitution effected by benzylic lithiation of ortho-tolyl-arylsulfones (26). The rearrangement is more broadly applicable to ipso-substitution reactions with aryl sulfides, sulfoxides, sulfones, and amides.…”

Optimized Conditions for Passerini-Smiles Reactions and Applications to Benzoxazinone Syntheses

“…Noteworthy is the special behavior of the dinitro compound 4c that decomposed under these conditions. Unfortunately, the reaction failed for Passerini-adducts derived from an aromatic As the chlorine atom was located at the para-position of the amide, a second Smiles rearrangement was involved and the spiro ring-opening probably occurred with concomittant substitution of the nitro by the released alkoxide (Scheme 15) [11][12][13][14]. Similar concerted processes have been clearly evidenced by theoretical calculations [15].…”

“…However, in this synthesis, the loss of the former isocyanide moiety reduces the molecular diversity traditionally associated with Passerini couplings. When considering the literature upon Smiles rearrangements, an impressive number of reactions involves the transfer of the aromatic moiety from an oxygen atom to the nitrogen atom of an amide under basic conditions [11][12][13]. Due to the structure of Passerini-Smiles adducts, we surmised that it could be possible to perform a second Smiles rearrangement in order to obtain N-aryl α-hydroxy carboxamides.…”

Benzylic C−H Functionalisation by [Et3SiH+KOtBu] leads to Radical Rearrangements in o‐tolyl Aryl Ethers, Amines and Sulfides

“…Given the evidence for triethylsilyl radicals in these reaction mixtures, this rearrangement looks to be a radical‐induced Truce‐Smiles rearrangement . Hydrogen atom abstraction from the methyl group of 19 forms radical 21 .…”