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.

Dihydroarylfuran skeletons are efficiently synthesized from (Z)-bromonitroalkenes and naphthol derivatives in good yields and excellent enantioselectivities by using squaramide catalysis.

An efficient and general copper(i)-catalyzed silylation of p-quinone-methides is described. Non-symmetric dibenzylic silanes are obtained in high yields under mild reaction conditions. These compounds can be used as bench-stable benzylic carbanion precursors.

GABA A receptors (GABA A Rs) are targets for important classes of clinical agents (e.g., anxiolytics, anticonvulsants, and general anesthetics) that act as positive allosteric modulators (PAMs). Previously, using photoreactive analogs of etomidate ([ 3 H]azietomidate) and mephobarbital [[ 3 H]1-methyl-5-allyl-5-(mtrifluoromethyl-diazirynylphenyl)barbituric acid ([ 3 H]R-mTFD-MPAB)], we identified two homologous but pharmacologically distinct classes of general anesthetic binding sites in the a1b3g2 GABA A R transmembrane domain at b 1-a 2 (b 1 sites) and a 1-b 2 /g 1-b 2 (b 2 sites) subunit interfaces. We now use competition photolabeling with [ 3 H]azietomidate and [ 3 H]R-mTFD-MPAB to identify para-substituted propofol analogs and other drugs that bind selectively to intersubunit anesthetic sites. Propofol and 4-chloro-propofol bind with 5-fold selectivity to b 1 , while derivatives with bulkier lipophilic substitutions [4-(tert-butyl)-propofol and 4-(hydroxyl(phenyl)methyl)-propofol] bind with ∼10-fold higher affinity to b 2 sites. Similar to R-mTFD-MPAB and propofol, these drugs bind in the presence of GABA with similar affinity to the a 1-b 2 and g 1-b 2 sites. However, we discovered four compounds that bind with different affinities to the two b 2 interface sites. Two of these bind with higher affinity to one of the b 2 sites than to the b 1 sites. We deduce that 4-benzoyl-propofol binds with .100-fold higher affinity to the g 1-b 2 site than to the a 1-b 2 or b 1-a 2 sites, whereas loreclezole, an anticonvulsant, binds with 5-and 100-fold higher affinity to the a 1-b 2 site than to the b 1 and g 1-b 2 sites. These studies provide a first identification of PAMs that bind selectively to a single intersubunit site in the GABA A R transmembrane domain, a property that may facilitate the development of subtype selective GABA A R PAMs.

The selective dimerization of CO2 into glycolaldehyde is achieved in a one-pot two-step process via formaldehyde as a key intermediate. The first step concerns the iron-catalyzed selective reduction of CO2 into formaldehyde via formation and controlled hydrolysis of a bis(boryl)acetal compound. The second step concerns the carbene-catalyzed C-C bond formation to afford glycolaldehyde. Both carbon atoms of glycolaldehyde arise from CO2 as proven by labelling experiment with 13 CO2. This hybrid organometallic/organic catalytic system employs mild conditions (1 atm of CO2, 25 °C to 80 °C in less than 3 h) and low catalytic loadings (1 % and 2.5%, respectively). Glycolaldehyde is obtained in 53% overall yield. The appealing reactivity of glycolaldehyde is exemplified i) in a dimerization process leading to C4 aldose compounds and ii) in a tri-component Petasis-Borono-Mannich reaction generating C-N and C-C bond in one process. applies to the smallest carbohydrate, we believe that the strategy presented herein could stimulate different fields of CO2 reduction.

The asymmetric synthesis of tricyclic compounds by the desymmetrization of cyclohexadienones is presented. The reaction tolerated a large variety of substituents at different positions of the cyclohexadienone, and heterocyclic rings of different sizes were accessible. Density functional theory calculations showed that the reaction proceeds through an asynchronous [4+2] cycloaddition.

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.

The hydroboration of CO2 into bis(boryl)acetal (BBA) compounds is an important transformation, since it enabled to selectively reduce CO2 by 4e‐ and to subsequently use the BBA compounds as C1 and Cn sources. However, the influence of the nature of the boryl moieties on the reactivity of BBA compounds has not been evaluated so far. In the present study, four BBA compounds – including two new ones – were reacted with 2,6‐diisopropylaniline to afford the expected imine. Significant differences in the rate of the reaction from minutes to weeks have been observed depending on the BBA used, showing the importance of the nature of the boryl moieties. Theoretical investigations enabled to propose a mechanism involving the addition of the aniline to the BBA as the rate‐determining step and to determine that the steric hindrance of the BBA compounds is the main factor driving the rate of this condensation reaction.