Advanced General Chemistry

Textbook adapted for CHM 118 at Smith College: This course is for students with a very strong background in chemistry. The elementary theories of stoichiometry, atomic structure, bonding, structure, energetics and reactions are quickly reviewed. The major portions of the course involve a detailed analysis of atomic theory and bonding from an orbital concept, an examination of the concepts behind thermodynamic arguments in chemical systems, and an investigation of chemical reactions and kinetics. The laboratory deals with synthesis, physical properties and kinetics.https://scholarworks.smith.edu/textbooks/1006/thumbnail.jp

One-pot anti-Markovnikov hydroamination of unactivated alkenes by hydrozirconation and amination.

A one-pot anti-Markovnikov hydroamination of alkenes is reported. The synthesis of primary and secondary amines from unactivated olefins was accomplished in the presence of a variety of functional groups. Hydrozirconation, followed by amination with nitrogen electrophiles, provides exclusive anti-Markovnikov selectivity. Most products are isolated in high yields without the use of column chromatography

Silver-Mediated Fluorination of Functionalized Aryl Stannanes

We report a regiospecific silver-mediated fluorination of aryl stannanes. The presented reaction can afford complex fluoroarenes from readily available phenols in three steps. The operational simplicity and the broad substrate scope of the fluorination should render this reaction a useful tool for the synthesis of milligram to gram quantities of functionalized aryl fluorides. Silver-mediated oxidative transformations of aryl nucleophiles that proceed via bimetallic redox processes are a new avenue to develop carbon−heteroatom bond formations.Chemistry and Chemical Biolog

Mechanism of C−F Reductive Elimination from Palladium(IV) Fluorides

The first systematic mechanism study of C−F reductive elimination from a transition metal complex is described. C−F bond formation from three different Pd(IV) fluoride complexes was mechanistically evaluated. The experimental data suggest that reductive elimination occurs from cationic Pd(IV) fluoride complexes via a dissociative mechanism. The ancillary pyridyl-sulfonamide ligand plays a crucial role for C−F reductive elimination, likely due to a κ^3 coordination mode, in which an oxygen atom of the sulfonyl group coordinates to Pd. The pyridyl-sulfonamide can support Pd(IV) and has the appropriate geometry and electronic structure to induce reductive elimination

Iron-Catalyzed Oxidative α-Amination of Ketones with Primary and Secondary Sulfonamides

We report the iron-catalyzed α-amination of ketones with sulfonamides. Using an oxidative coupling approach, ketones can be directly coupled with free sulfonamides, without the need for prefunctionalization of either substrate. Primary and secondary sulfonamides are both competent coupling partners, with yields from 55% to 88% for deoxybenzoin-derived substrates

Mechanism of Iron-Catalyzed Oxidative α-Amination of Ketones with Sulfonamides

We report the mechanism of the iron-catalyzed oxidative α-amination of ketones with sulfonamides. Using linear free energy relationships, competition experiments, and identification of reaction intermediates, we have found that the mechanism of this reaction proceeds through rate-limiting electron transfer to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) from an iron enolate in the process of forming an α-DDQ adduct. The adduct then serves as the electrophile for substitution with sulfonamide nucleophiles, accelerated by iron and additional DDQ. This mechanistic study rules out formation of an α-carbocation intermediate and purely radical mechanistic hypotheses

Mechanism of C−F Reductive Elimination from Palladium(IV) Fluorides

The first systematic mechanism study of C−F reductive elimination from a transition metal complex is described. C−F bond formation from three different Pd(IV) fluoride complexes was mechanistically evaluated. The experimental data suggest that reductive elimination occurs from cationic Pd(IV) fluoride complexes via a dissociative mechanism. The ancillary pyridyl-sulfonamide ligand plays a crucial role for C−F reductive elimination, likely due to a κ3 coordination mode, in which an oxygen atom of the sulfonyl group coordinates to Pd. The pyridyl-sulfonamide can support Pd(IV) and has the appropriate geometry and electronic structure to induce reductive elimination.Chemistry and Chemical Biolog