Micellar catalysis enables copper-catalyzed silylcupration of a variety of electron-deficient alkynes, thereby providing access to isomerically pure E- or Z-β-silyl-substituted carbonyl derivatives. These reactions take place in minutes, afford high yields and stereoselectivity, and are especially tolerant of functional groups present in the substrates. The aqueous reaction medium has been successfully recycled several times, and a substrate/catalyst ratio of 10,000:1 has been documented for this methodology.

Reported is the first nickel-catalyzed enantioselective allylic alkylation of lactones and lactams to provide products bearing an all-carbon quaternary stereocenter.

Cation‐binding salen nickel catalysts were developed for the enantioselective alkynylation of trifluoromethyl ketones in high yield (up to 99 %) and high enantioselectivity (up to 97 % ee). The reaction proceeds with substoichiometric quantities of base (10–20 mol % KOt‐Bu) and open to air. In the case of trifluoromethyl vinyl ketones, excellent chemo‐selectivity was observed, generating 1,2‐addition products exclusively over 1,4‐addition products. UV‐vis analysis revealed the pendant oligo‐ether group of the catalyst strongly binds to the potassium cation (K+) with 1:1 binding stoichiometry (Ka=6.6×105 m−1).

Herein, we report the first Pd‐catalyzed enantioselective arylation of α‐substituted γ‐lactams. Two sets of conditions were developed for this transformation, allowing for the use of either aryl chlorides or bromides as electrophiles. Utilizing a highly electron‐rich dialkylphosphine ligand we have been able to construct α‐quaternary centers in good yields (up to 91 % yield) and high enantioselectivities (up to 97 % ee).

Herein, we report aC u-catalyzed enantioselective allylic alkylation using a g-butyrolactone-derived silyl ketene acetal. Critical to the development of this work was the identification of an ovel mono-picolinamide ligand with the appropriate steric and electronic properties to affordt he desired products in high yield (up to 96 %) and high ee (up to 95 %). Aryl, aliphatic,a nd unsubstituted allylic chlorides bearing ab road range of functionality are well-tolerated. Spectroscopic studies reveal that aC u I species is likely the active catalyst, and DFT calculations suggest ligand sterics play an important role in determining Cu coordination and thus catalyst geometry.

Materials and Methods Unless otherwise stated, reactions were performed in flame-dried glassware under an argon or nitrogen atmosphere using dry, deoxygenated solvents. Solvents were dried by passage through an activated alumina column under argon. Reaction progress was monitored by thin-layer chromatography (TLC) or Agilent 1290 UHPLC-MS. TLC was performed using E. Merck silica gel 60 F254 precoated glass plates (0.25 mm) and visualized by UV fluorescence quenching, p-anisaldehyde, or KMnO 4 staining. Silicycle SiliaFlash® P60 Academic Silica gel (particle size 40-63 nm) was used for flash chromatography. 1 H NMR spectra were recorded on a Bruker Avance HD 400 MHz or Varian Mercury 300 MHz spectrometers and are reported relative to residual CHCl 3 (δ 7.26 ppm). 13 C NMR spectra were recorded on a Bruker Avance HD 400 MHz spectrometer (100 MHz) and are reported relative to residual CHCl 3 (δ 77.36 ppm). 19 F NMR spectra were recorded on a Varian Mercury 300 MHz spectrometer (282 MHz). Data for 1 H NMR are reported as follows: chemical shift (δ ppm) (multiplicity, coupling constant (Hz), integration). Multiplicities are reported as follows: s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sept = septuplet, m = multiplet, br s = broad singlet, br d = broad doublet, app = apparent. Data for 13 C NMR are reported in terms of chemical shifts (δ ppm). IR spectra were obtained using a Perkin Elmer Spectrum BXII spectrometer or Nicolet 6700 FTIR spectrometer using thin films deposited on NaCl plates and reported in frequency of absorption (cm-1). Optical rotations were measured with a Jasco P-2000 polarimeter operating on the sodium D-line (589 nm), using a 100 mm path-length cell and are reported as: [α] D T (concentration in 10 mg/1 mL, solvent). Analytical SFC was performed with a Mettler SFC supercritical CO 2 analytical chromatography system utilizing Chiralpak (AD-H) or Chiralcel (OD-H) columns (4.6 mm x 25 cm) obtained from Daicel Chemical Industries, Ltd. High resolution mass spectra (HRMS) were obtained from Agilent 6200 Series TOF with an Agilent G1978A S3 Multimode source in electrospray ionization (ESI+), atmospheric pressure chemical ionization (APCI+), or mixed ionization mode (MM: ESI-APCI+). Reagents were purchased from Sigma-Aldrich, Acros Organics, Strem, or Alfa Aesar and used as received unless otherwise stated. List of Abbreviations ee-enantiomeric excess, SFC-supercritical fluid chromatography, TLC-thin-layer chromatography, IPA-isopropanol, MTBE-methyl tert-butyl ether, PE-petroleum ether, DMAP-4-dimethylaminopyridine, EtOAc-ethyl acetate, LiHMDS-lithium bis(trimethylsilyl)amide, NaHMDS-sodium bis(trimethylsilyl)amide, PMPp-methoxy phenyl, pmdba-4,4'-dimethoxydibenzylideneacetone, THF-tetrahydrofuran, DMEDA-1,2-dimethylethylenediamine.

Nonracemically ligated copper hydride can be used to effect tandem S2'/1,2-reductions of racemic Morita-Baylis-Hillman (MBH) acetates to access enantioenriched chiral allylic alcohols with defined olefin geometry. MBH esters, including those with β-substitution, can be transformed to stereodefined enoates by taking advantage of a bulky, oligomeric, in situ generated trialkoxysiloxane leaving group. Finally, an atypical conversion of easily arrived at MBH alcohol derivatives to nonracemic allylic alcohols is disclosed.

Micellar catalysis enables copper-catalyzed silylcupration of a variety of electron-deficient alkynes, thereby providing access to isomerically pure E-or Z-b-silyl-substituted carbonyl derivatives. These reactions take place in minutes, afford high yields and stereoselectivity, and are especially tolerant of functional groups present in the substrates. The aqueous reaction medium has been successfully recycled several times, and a substrate/catalyst ratio of 10,000:1 has been documented for this methodology.