The work described here represents the first example of an enantiopure hybrid scorpionate/cyclopentadiene ligand. The ligand was obtained in a one-pot synthetic procedure by an efficient and highly diastereoselective nucleophilic addition of an organolithium reagent to an electrophilically activated olefin in a new fulvene with a chiral substrate to control the stereochemistry of a newly created asymmetric center. We verified the potential utility of this ligand as a valuable scaffold that is able to induce chirality in organometallic/coordination chemistry. This was achieved through the preparation of a new enantiomerically pure zinc complex in which the ligand behaves in a tridentate manner with a κ2 NN-η1(π)-Cp coordination mode. This alkylzinc complex constitutes the first example of an organozinc derivative which behaves as an efficient initiator for the ROP of rac-LA in the production of isotactic-enriched poly(lactides) with P i = 0.77.

The preparation of the first racemic bis(pyrazol-1-yl)methane-based NNCp-donor hybrid scorpionate/cyclopentadienyl magnesium and zinc complexes [Mg(R)(κ 2 -η 5 -NNCp)] (1−6) [NNCp = bpztcp, R = Me (1), Et (2), CH 2 SiMe 3 (3); bpzpcp, R = Me (4), Et (5), CH 2 SiMe 3 (6)] and [Zn(R)(κ 2 -η 1 -NNCp)] (7−12) [NNCp = bpztcp, R = Me (7), Et (8), CH 2 SiMe 3 (9); bpzpcp, R = Me (10)

1,1,1-Trifluoroacetone (2a) reacts as a hydride-acceptor in the Oppenauer oxidation of secondary alcohols (1) in the presence of diethylethoxyaluminum. The oxidant allows for selective oxidation of secondary alcohols in the presence of primary alcohols.

Amazing reaction medium: Supercritical carbon dioxide, with zero dipole moment, lower dielectric constant than pentane, and non‐hydrogen‐bonding behavior, ionizes carbon–halogen bonds, dissociates the resulting ion pairs, and escapes from capture by the carbocation intermediates at temperatures above 40 °C. These properties allow the observation of carbocation chemistry in the absence of acids.

No solvent, no reaction: ethanol inhibits SN1 reactions of alkyl halides in scCO2 by competing with the substrate for solvation.