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The selective double hydroboration of CO 2 into bis(boryl)acetal (BBA) is a challenging yet appealing reduction process since BBA can be used as a versatile C 1 and C n sources for the synthesis of value-added products. In the present study, we demonstrate that simple borohydride compounds are efficient and selective catalysts for the synthesis of BBA when using 9-borabicyclo(3.3.1)nonane (9-BBN) as a reductant. The experimental and theoretical investigations show that while the borohydride species catalyzes the first reduction step of CO 2 into formoxyborane (2e - reduction intermediate), the observed 4e - reduction selectivity is mostly due to the ability of 9-BBN to reduce the formoxyborane into BBA without a catalyst. Notably, 0.2 mol % of LiH 2 BBN catalyzed the hydroboration of CO 2 with 9-BBN as a reductant into the corresponding BBA in 77% yield with TON and TOF of 385 and 196 h -1 , respectively. The simplicity of borohydride contrasts with the more elaborate catalytic systems used so far for the 4e - reduction of CO 2 .

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-( m -trifluoromethyl-diazirynylphenyl)barbituric acid ([ 3 H] R - m TFD-MPAB)], we identified two homologous but pharmacologically distinct classes of general anesthetic binding sites in the α 1 β 3 γ 2 GABA A R transmembrane domain at β + - α - ( β + sites) and α + - β - / γ + - β - ( β - sites) subunit interfaces. We now use competition photolabeling with [ 3 H]azietomidate and [ 3 H] R-m TFD-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 β + , while derivatives with bulkier lipophilic substitutions [4-( tert -butyl)-propofol and 4-(hydroxyl(phenyl)methyl)-propofol] bind with ∼10-fold higher affinity to β - sites. Similar to R-m TFD-MPAB and propofol, these drugs bind in the presence of GABA with similar affinity to the α + - β - and γ + - β - sites. However, we discovered four compounds that bind with different affinities to the two β - interface sites. Two of these bind with higher affinity to one of the β - sites than to the β + sites. We deduce that 4-benzoyl-propofol binds with >100-fold higher affinity to the γ + - β - site than to the α + - β - or β + - α - sites, whereas loreclezole, an anticonvulsant, binds with 5- and 100-fold higher affinity to the α + - β - site than to the β + and γ + - β - 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., (Copyright © 2019 by The American Society for Pharmacology and Experimental Therapeutics.)

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., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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.

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.

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., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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