Gabriela Méndez-Abt

A Convenient Domino Access to Substituted Alkyl 1,2‐Dihydropyridine‐3‐carboxylates from Propargyl Enol Ethers and Primary Amines

This research was supported by the Spanish Ministerio de Ciencia e Innovacion, the European Regional Development Fund (CTQ2005-09074-C02-02 and CTQ2008-06806-C02-02) and the Spanish MSC ISCIII (RETICS, RD06/0020/1046, and RD06/0020/0041), CSIC (Proyecto Intramural Especial 200719), FUNCIS (REDESFAC PI01/06 and 35/06) and the Fundacion Instituto Canario de Investigacion del Cancer (FICI-G.I.N808/2007). G.M.-A. thanks Spanish MEC for a FPU grant.

Acetylides from Alkyl Propiolates as Building Blocks for C3 Homologation

Alkyl propiolates are reagents with a versatile reactivity profile that entirely remains in the C(3)-homologated product for further elaboration. To be effective, this C(3) homologation requires suitable methods for the generation of the acetylide anion that are compatible with both the conjugated ester and the electrophilic partner. Recent advances include catalytic procedures for the in situ generation of these acetylides in the presence of suitable electrophiles. Whereas the organometallic methods have brought stereoselectivity to these reactions, the organocatalytic methods laid the ground for new efficient domino processes that generate complexity.

A Microwave‐Assisted Domino Rearrangement of Propargyl Vinyl Ethers to Multifunctionalized Aromatic Platforms

This research was supported by the Spanish MICINN and the European RDF (CTQ2008-06806-C02-01 and CTQ2008-06806-C02-02), the Spanish MSC ISCIII (RETICS RD06/0020/1046), FUNCIS (REDESFAC PI01/06). G.M.A. and L.C. thank the Spanish MEC for FPU and FPI grants, respectively. The authors thank Dr. T. Martin and Professor V. S. Martin for insightful discussions, Professor F. Cossio for mechanistic advice, and Anna Jurado for technical assistance.

General Synthesis of Substituted 1,2-Dihydropyridines

A general and practical metal-free protocol for the synthesis of 1,2-dihydropyridines with wide structural/functional diversity at the ring and featuring mono, double, or spiro substitution at the sp(3) position is described. The protocol entails a microwave-assisted domino reaction of a propargyl vinyl ether (secondary or tertiary) and a primary amine (aliphatic or aromatic) in toluene or methanol.

Merging domino and redox chemistry: stereoselective access to di- and trisubstituted β,γ-unsaturated acids and esters.

Merging is the game! The coupling of a domino reaction and an internal neutral redox reaction constitutes an excellent manifold for the stereoselective synthesis of di- and trisubstituted olefins featuring a malonate unit, an ester, or a free carboxylic acid as substituents at the allylic position (see scheme; MW=microwave). The reaction utilizes simple starting materials (propargyl vinyl ethers), methanol or water as solvents, and a very simple and bench-friendly protocol.