Mariola Tortosa

para‐Quinone Methide: a New Player in Asymmetric Catalysis

This is the accepted version of the following article: Parra, A. and Tortosa, M. (2015), para-Quinone Methide: a New Player in Asymmetric Catalysis. ChemCatChem, 7: 1524–1526, which has been published in final form at http://dx.doi.org/10.1002/cctc.201500176. This article may be used for non-commercial purposes in accordance with the Wiley Self-Archiving Policy wiley.com/WileyCDA/Section/id- 820227.html

Arylsulfonylacetylenes as Alkynylating Reagents of C sp 2H Bonds Activated with Lithium Bases

Chameleon: a new strategy for the synthesis of a wide variety of alkynyl derivatives by the reaction of substituted arylsulfonylacetylenes with organolithium species is described. The high yields, the simplicity of the experimental procedure, the broad scope of this reaction, and the formation of C(sp)-C(sp2) bonds without using transition metals are the main features of this methodology.

Expanding the Scope of Arylsulfonylacetylenes as Alkynylating Reagents and Mechanistic Insights in the Formation of Csp2Csp and Csp3Csp Bonds from Organolithiums

We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an anti-Michael addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results can be achieved by theoretical calculations, which suggest that the association of the organolithiums to the electrophile is a previous step of their intramolecular attack and is responsible for the unexpected anti-Michael reactions observed for substituted sulfonylacetylenes.

Enantioselective Synthesis of Cyclobutylboronates via a Copper‐Catalyzed Desymmetrization Approach

The first catalytic enantioselective synthesis of cyclobutylboronates, by using a chiral copper(I) complex, is reported. A broad variety of cyclobutanes have been prepared with consistently high levels of diastereo- and enantiocontrol. Moreover, this method constitutes the first report of an enantioselective desymmetrization of meso-cyclobutenes to prepare chiral cyclobutanes.

Copper-catalysed cross-coupling of alkyl Grignard reagents and propargylic ammonium salts: stereospecific synthesis of allenes

Herein we describe a robust and practical method to prepare enantiomerically enriched trisubstituted allenes using alkyl Grignard reagents and bench stable propargylic ammonium salts. Excellent yields as well as regio- and stereoselectivities are observed. Our conditions provide a solution to the allene racemization, which has been a long-standing problem when using Grignard reagents.

Stereoselective Traceless Borylation–Allenation of Propargylic Epoxides: Dual Role of the Copper Catalyst

Chiral α-allenols are prepared with high diastereocontrol through an unprecedented and spontaneous β-oxygen elimination of an α-epoxy vinyl boronate. Stochiometric experiments and DFT calculations support a dual role of the copper catalyst, which orchestrates the hydroboration and the syn-elimination step.