Multicomponent synthesis of α-branched amines using organozinc reagents generated from alkyl bromides.

The use of alkylzinc bromides in the multicomponent Mannich reaction is described. Heteroleptic organozinc compounds were obtained in THF or 2-MeTHF by direct insertion of zinc dust into the C-Br bond of alkyl bromides. It was found that the presence of a stoichiometric amount of LiCl was essential for the efficiency of the subsequent three-component coupling with aldehydes and amines.

Trans-Concerted Addition to Alkynes: the case of Ynamide Silylzincation.

An original concerted antarafacial mechanism for the addition of diorganosilyl-zinc reagents across the C-C triple bond of ynamides is computationally investigated using DFT calculations. This concerted mechanism, leading to a trans-product in only one step, results in the formation of a Si-C and a Zn-C σ-bond on opposite sides of the π-system. We demonstrate that the mechanism going through a η-vinyl intermediate and the proposal of a radical chain pathway are energetically unsustainable.

α-(Aminomethyl)acrylates as acceptors in radical-polar crossover 1,4-additions of dialkylzincs: insights into enolate formation and trapping.

We demonstrate that α-(aminomethyl)acrylates are suitable acceptors for 1,4-additions of dialkylzincs in aerobic conditions. The air-promoted radical-polar crossover process involves the 1,4-addition of an alkyl radical followed by homolytic substitution at the zinc atom of dialkylzinc. Coordination of the nitrogen atom to zinc enables this S2 process which represents a rare example of alkylzinc-group transfer to a tertiary α-carbonyl radical.

Enantioselective Sequential Catalytic Arylation-Fukuyama Cross-coupling of 1,1-Biszincioalkane Linchpins.

1,1-Bis(iodozincio)alkanes are used as dinucleophilic linchpins in an enantioselective double cross-coupling reaction sequence involving aryl iodides and then thioesters. The two catalytic C-C bond-forming reactions are achieved in the same pot through two distinct palladium-based catalytic systems: a first non-enantioselective one delivering configurationally labile secondary benzylzinc species from an achiral precursor, and a second enantioconvergent one that operates a highly efficient dynamic kinetic resolution of the racemic intermediates. This strategy, new in the area of asymmetric synthesis through two consecutive electrophilic substitution reactions of geminated C(sp )-organodimetallics, provides useful methodology to access in a modular fashion acyclic α-disubstituted ketone products with very high enantiomeric purity.

Knowledge and Opinions of French Dental Students in Operative Dentistry - Management of Deep Carious Lesions.

Purpose: A questionnaire survey was recently undertaken among French dental students (FDSs) to investigate their practices, knowledge and opinions in various domains of minimal intervention (MI) in cariology. The present work focuses on management of deep carious lesions (DCLs).

Materials And Methods: The questionnaire was administered (Spring 2018) to all the fifth-year students of the 16 French dental schools.