A Tandem Enol Silane Formation-Mukaiyama Aldol Reaction Mediated by TMSOTf

A slight excess of silyl trifluoromethanesulfonate mediates a tandem enol silane formation-Mukaiyama aldol reaction in the presence of Hunig’s base. Preformation of the enol silane is unnecessary for efficient reactions, which proceed in 75–97% yield for the addition of aryl methyl ketones and acetate esters to non-enolizable aldehydes. Mechanistic data suggests that free amine is crucial for full conversion

One-Pot Enol Silane Formation-Mukaiyama Aldol-Type Addition to Dimethyl Acetals Mediated by TMSOTf

Various ketones, esters, amides, and thioesters add in high yield to dimethyl acetals in the presence of silyl trifluoromethanesulfonates and an amine base. Acetals derived from aryl, unsaturated, and aliphatic aldehydes are all effective substrates. The reaction proceeds in a single reaction flask, with no purification of the intermediate enol silane necessary

Flora of Richmond National Battlefield Park, Virginia

An inventory of the vascular flora of nine of eleven units of Richmond National Battlefield Park was compiled from 1985 to 1987. Each site was visited during the growing season in two to four week intervals; plant species were identified and recorded in the field and/or collected for later study. A total of 761 different species were identified in the surveyed units, and 2487 individual records of species per particular park unit were noted. Twenty-three percent of the flora consists of exotic species, largely from Eurasia. Voucher specimens are housed in the herbaria of the University of Richmond and Virginia Commonwealth University

Accommodation of lattice mismatch in Ge_(x)Si_(1−x)/Si superlattices

We present evidence that the critical thickness for the appearance of misfit defects in a given material and heteroepitaxial structure is not simply a function of lattice mismatch. We report substantial differences in the relaxation of mismatch stress in Ge_(0.5)Si_(0.5)/Si superlattices grown at different temperatures on (100) Si substrates. Samples have been analyzed by x‐ray diffraction, channeled Rutherford backscattering, and transmission electron microscopy. While a superlattice grown at 365 °C demonstrates a high degree of elastic strain, with a dislocation density <10^5 cm^(−2) , structures grown at higher temperatures show increasing numbers of structural defects, with densities reaching 2×10^(10) cm^(−2) at a growth temperature of 530 °C. Our results suggest that it is possible to freeze a lattice‐mismatched structure in a highly strained metastable state. Thus it is not surprising that experimentally observed critical thicknesses are rarely in agreement with those predicted by equilibrium theories

A mechanistic investigation of the photoinduced, copper-mediated cross-coupling of an aryl thiol with an aryl halide

Photoinduced, copper-catalyzed cross-coupling can offer a complementary approach to thermal (non-photoinduced) methods for generating C–X (X = C, N, O, S, etc.) bonds. In this report, we describe the first detailed mechanistic investigation of one of the processes that we have developed, specifically, the (stoichiometric) coupling of a copper–thiolate with an aryl iodide. In particular, we focus on the chemistry of a discrete [Cu^I(SAr)_2]− complex (Ar = 2,6-dimethylphenyl), applying a range of techniques, including ESI-MS, cyclic voltammetry, transient luminescence spectroscopy, optical spectroscopy, DFT calculations, Stern–Volmer analysis, EPR spectroscopy, actinometry, and reactivity studies. The available data are consistent with the viability of a pathway in which photoexcited [Cu^I(SAr)_2]−* serves as an electron donor to an aryl iodide to afford an aryl radical, which then reacts in cage with the newly generated copper(II)–thiolate to furnish the cross-coupling product in a non-chain process

Acetic Acid Aldol Reactions in the Presence of Trimethylsilyl Trifluoromethanesulfonate

In the presence of TMSOTf and a trialkylamine base, acetic acid undergoes aldol addition to non-enolizable aldehydes under exceptionally mild conditions. Acidic workup yields the β-hydroxy carboxylic acid. The reaction appears to proceed via a three-step, one-pot process, including in situ trimethylsilyl ester formation, bis-silyl ketene acetal formation, and TMSOTf-catalyzed Mukaiyama aldol addition. Independently synthesized TMSOAc also undergoes aldol additions under similar conditions

Enantioselective, Stereodivergent Hydroazidation and Hydroamination of Allenes Catalyzed by Acyclic Diaminocarbene (ADC) Gold(I) Complexes

The gold-catalyzed enantioselective hydroazidation and hydroamination reactions of allenes are presented herein. ADC gold(I) catalysts derived from BINAM were critical for achieving high levels of enantioselectivity in both transformations. The sense of enantioinduction is reversed for the two different nucleophiles, allowing access to both enantiomers of the corresponding allylic amines using the same catalyst enantiomer