A reaction in its own right is the Ugi–Smiles reaction with the carboxylic acid component replaced by a phenol. In this reaction the Mumm rearrangement in the final step is replaced by the Smiles rearrangement.

2014年10月19日 · The Ugi–Smiles and Passerini–Smiles couplings are isocyanide-based multicomponent reactions involving phenols and each featuring a Smiles rearrangement as a key step of the mechanism. Their scope, mechanistic studies, and the use of these couplings for a variety of routes to fused aromatic systems are reviewed here.

This reaction, termed the phenol Ugi–Smiles system, leverages electron-deficient phenols to activate imines and induce irreversible rearrangements, resulting in the efficient formation of N -aryl amines. The reaction proceeds smoothly under mild conditions, yielding high amounts of the desired products.

2007年4月25日 · The use of Smiles rearrangement in Ugi- and Passerini-type couplings with electron-deficient phenols allows very straightforward multicomponent formation of O -aryl- and N -arylamides. Best yields were observed with the highly activated o- and p -nitrophenols, salicylic derivatives giving adducts in lower yields.

A Smiles rearrangement is the key step in the efficient coupling of primary amines with isocyanides, carbonyl compounds, and electron-deficient substituted phenols to form N -aryl amines (see picture). The presence of a nitro or ester group on the resulting adduct allows applications in heterocyclic synthesis.

2007年6月22日 · A new strategy involving Ugi-Smiles coupling followed by ring-closure metathesis is described herein for the preparation of pyrimidine-fused heterocyclic scaffolds. The scope of this sequence is presented in relation with the heteroatom effect observed in the Ugi-Smiles coupling.

2014年9月26日 · The mechanisms of the Ugi and Ugi–Smiles reactions were investigated by using finely selected reaction conditions that allowed all of the intermediates to be “fish-out” and characterized by ESI-MS/MS.

2009年7月7日 · Various organometallic reactions of the Ugi–Smiles adducts have been successfully carried out, either from iodophenols (Heck couplings to give indoles, Ullmann reaction to form quinoxalines), or from allyl pyrimidines (azepine formation by RCM strategy) as starting phenol inputs.

2014年10月18日 · The Ugi–Smiles couplings and Passerini–Smiles couplings of phenols and mercaptan offer new four-component access to N-aryl and O-aryl derivatives. Since the Passerini–Smiles coupling offers less diversity, most efforts were devoted to Ugi–Smiles adducts, focusing on transformations involving the newly introduced aryl moieties in order ...

2013年7月25日 · In a recent communication, we described the mechanism of the well-known Ugi-type reactions with a model system ( J. Org. Chem. 2012, 77, 1361−1366). Herein, focusing on the Ugi–Smiles coupling, we study the effects of each of the four reactants on the energy profile to further explain the experimental results.