Damien Prim

Design and Synthesis of New Circularly Polarized Thermally Activated Delayed Fluorescence Emitters

This work describes the first thermally activated delayed fluorescence material enabling circularly polarized light emission through chiral perturbation. These new molecular architectures obtained through a scalable one-pot sequential synthetic procedure at room temperature (83% yield) display high quantum yield (up to 74%) and circularly polarized luminescence with an absolute luminescence dissymmetry factor, |glum|, of 1.3 × 10(-3). These chiral molecules have been used as an emissive dopant in an organic light emitting diode exhibiting external quantum efficiency as high as 9.1%.

Highly stereoselective ring expansion of enantiopure α-hydroxyalkyl azetidines

Abstract Stereodefined α-hydroxyalkyl azetidines, prepared in a few steps from enantiopure β-amino alcohols, are chlorinated or transformed into methanesulfonyloxymethyl derivatives in good yields. Heating of these compounds in chloroform or dimethylformamide induces a stereospecific ring enlargement to give 3-chloro or 3-methanesulfonyloxy pyrrolidines. The ease of this rearrangement depends on the nature of the migrating group (Cl − or MsO − ), of the class of the starting alcohol (primary or secondary) and of the relative stereochemistry of the starting material.

Synthesis of enantiopure 2-acyl azetidines and the application of amino alcohols derived therefrom in enantioselective catalysis

Enantiopure 2-acyl azetidines were prepared in good yields from 2-cyano azetidines. The ketones produced were then stereoselectively reduced with sodium borohydride (with or without zinc bromide) or transformed into tertiary azetidinic amino alcohols by addition of phenyllithium. The latter compounds were found to be highly efficient catalysts for the enantioselective addition of diethylzinc to aldehydes, giving enantioselectivities up to 98%.

First expeditious synthesis of 6,11-diamino-[6]carbohelicenes

The first synthesis of 6,11-diamino-[6]carbohelicenes is described: the short 5 step sequence involves Suzuki-Miyaura coupling, functional group transformations and electrophilic aromatic cyclisation; the original strategy allows the preparation of di- and tetra-substituted helicenes in comfortable yields.

Regio-Defined Amino[5]Oxa- and Thiahelicenes: A Dramatic Impact of the Nature of the Heteroatom on the Helical Shape and Racemization Barriers

The present approach to heterohelicenes provides original [5]oxa- and thiahelicenes, where both oxygen and sulfur atoms are located at the end of the inner helix. Quantum chemical calculations are carried out to determine the pathway for interconversion between two enantiomers and demonstrate that the energy barrier is strongly dependent on the nature of the heteroatom present on the helical shape.

Concise Synthesis of Tricyclic Isoindolinones via One-Pot Cascade Multicomponent Sequences

A series of enantiopure tricyclic isoindolinones has been successfully synthesized through a one-pot selective cascade process from furan derivatives. The synthesis is straightforward and gave good overall yields taking into account the concomitant formation of five C-C, C-O, and C-N bonds. The strategy was extended to the preparation of a thiazolidine analogue.

Synthesis of nitrile ligands bearing tricarbonyl (η6-arene)chromium complexes and conjugated spacers

Abstract The synthesis of nitrile ligands linked to tricarbonyl (η 6 -arene)chromium complexes by conjugated spacers is performed by reacting aromatic bromo nitrile derivatives with tricarbonylchromium-complexed phenylacetylene using Sonogashira coupling reaction.

General Access to Aminobenzyl-o-carboranes as a New Class of Carborane Derivatives: Entry to Enantiopure Carborane–Amine Combinations

The convenient synthesis of original aminobenzyl-o-carboranes, which represent a new class of nitrogenated carborane derivatives, is described. These novel compounds have been efficiently prepared starting from commercially available aromatic aldehydes and monosubstituted o-carboranes via carboranyl alcohols and chlorides as intermediates. The key step of this methodology is a selective nucleophilic amination under mild conditions that allows the formation of the expected amines while limiting the partial deboronation of the carborane cluster. This general strategy has been applied to the preparation of a wide variety of aminobenzyl-o-carboranes. The extension of this pathway to the synthesis of enantiopure carborane-amine combinations is also described.

Organochromium/organoiron dipoles comprising (η6-arene)chromium and (η5-cyclohexadienyl)iron(1+) complexes linked with conjugated spacers

Abstract The synthesis of novel bimetallic organochromium/organoiron monocation dipoles comprising π-conjugated complexes linked with conjugated spacers has been performed utilising Stille and Sonogashira coupling reactions. This work establishes a general strategy for the synthesis of mixed-metal chromium/dipole complexes for evaluation for nonlinear optical effects by hyper-Rayleigh scattering.

Binaphthyl platform as starting materials for the preparation of electron rich benzo[g,h,i]perylenes. Application to molecular architectures based on amino benzo[g,h,i]perylenes and carborane combinations

Valuable amino benzo[g,h,i]perylenes have been obtained through a one pot electrophilic aromatic substitution--Scholl reaction sequence. Novel molecular architectures combining 3D-o-carborane and planar amino benzo[g,h,i]perylene units are described. Photophysical properties of amino benzo[g,h,i]perylene and the carborane-appended derivatives are discussed.