On the mechanism of the formation of alkyl-Ni(I) catalysts.

The formation of catalytically active alkyl-Ni(i) complexes by comproportionation of diorgano-Ni(ii) precursors and Ni(0) species proceeds easily through triplet states by alkyl ligand exchange. The process involves inversion of the configuration at the carbon that is transferred.

Ligand-Controlled Electron Structure of Catalytically Active Ni Complexes.

We have performed a systematic study of the electron structure of a series of Ni(I) and Ni(II) iodo and methyl complexes with a variety of di- and tridentate nitrogen ligands to study the influence of these ligands in the structure of catalytically active complexes in cross-coupling reactions. Ni(II) compounds show the expected square-planar configuration typical of complexes of d8 metals, regardless of the kind of coordinating nitrogen atom (sp2 or sp3) found in ligands derived from either trialkylamines or pyridines. In contrast, Ni(I) complexes show different structures. Thus, the absence of orbitals capable of delocalizing the unpaired electron (such as in TMEDA and PMDTA derivatives) leads to nonplanar iodo or methyl tetracoordinate complexes. In contrast, the presence of ligands derived from pyridine allows delocalization of the unpaired electron on the ligand. This delocalization is especially effective for terpyridine species.

Copper-Catalyzed Borylative Aromatization of p-Quinone Methides: Enantioselective Synthesis of Dibenzylic Boronates.

In this report, we establish that DM-Segphos copper(I) complexes are efficient catalysts for the enantioselective borylation of para-quinone methides. This method provides straightforward access to chiral monobenzylic and dibenzylic boronic esters, with enantiomeric ratios up to 96:4, using a commercially available chiral phosphine. Standard manipulations of the C-B bond afford a variety of chiral diaryl derivatives.

Nonafluorobutanesulfonyl azide as a shelf-stable highly reactive oxidant for the copper-catalyzed synthesis of 1,3-diynes from terminal alkynes.

Nonafluorobutanesulfonyl azide is a highly efficient reagent for the copper-catalyzed coupling of terminal alkynes to give symmetrical and unsymmetrical 1,3-diynes in good to excellent yields and with good functional group compatibility. The reaction is extremely fast (<10 min), even at low temperature (−78 °C), and requires substoichiometric amounts of a simple copper(I) or copper(II) salt (2­5 mol %) and an organic base (0.6 mol %). A possible mechanistic pathway is briefly discussed on the basis of model DFT theoretical calculations. The quantitative assessment of the safety of use and shelf stability of nonafluorobutanesulfonyl azide has confirmed that this reagent is a superior and safe alternative to other electrophilic azide reagents in use today.

Titanocene(III)-catalyzed 6-exo versus 7-endo cyclizations of epoxypolyprenes: efficient control and synthesis of versatile terpenic building blocks.

In this article, a complete study on the selectivity of titanocene(III) cyclization of epoxypolyprenes is presented. The requirements for the formation of six- or seven-membered rings during these cyclizations are determined, taking into account the different substitution pattern in the epoxypolyprene precursor. Thus, a complete selectivity to 6-exo or 7-endo cyclization process has been achieved, yielding mono-, bi-, and even tricyclic compounds, constituting a new and efficient access to this type of derivative. Additionally, this procedure opens the possibility to prepare excellent building blocks for the synthesis of polycyclic compounds with a trisubstituted oxygenated function, which is present in several natural terpenes.

Ni-catalyzed cascade cyclization-Kumada alkyl-alkyl cross-coupling.

Suggesting novel disconnections: A powerful Ni-catalyzed cascade reaction involving cyclization followed by cross-coupling allows the formation of up to three alkyl-alkyl bonds in a single operation by using alkene-containing alkyl iodides and Grignard reagents (see scheme; acac = acetylacetonate; TMEDA = N,N',N'-tetramethyl ethylenediamine). Mechanistic experimental and computational studies suggest a Ni(I)-Ni(II)-Ni(III) catalytic cycle and the intermediacy of radicals.

Pd-catalyzed borylative cyclisation of 1,7-enynes.

Reaction of a variety of 1,7-enynes with bis(pinacolato) diboron catalysed by Pd bis(trifluoroacetate) affords homoallylic and allylic boronates containing a six membered carbo- or heterocycle, by formation of C-C and C-B bonds.

Combining the power of Ti(III)-mediated processes for easy access to hydroxylated polycyclic terpenoids: synthesis of sesterstatin 1 and C-D rings of aspergilloxide.

A straightforward access to polyhydroxylated terpenoids based on two key titanocene(III)-mediated reactions is presented: the "head-to-tail" Barbier-type addition of prenyl chlorides to α,ß-unsaturated aldehydes, which allows the introduction of hydroxy groups at desirable positions of the acyclic precursor, and the subsequent bioinspired radical cyclisation. This methodology has been also used in the first total synthesis of pentacyclic sesterstatin 1 and a model compound of the C-D rings of aspergilloxide.