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 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.