Jennifer M. Schomaker

Bio: Jennifer M. Schomaker is an academic researcher from University of Wisconsin-Madison. The author has contributed to research in topics: Allene & Nitrene. The author has an hindex of 32, co-authored 137 publications receiving 2432 citations. Previous affiliations of Jennifer M. Schomaker include Michigan State University & Wisconsin Alumni Research Foundation.

Tunable, Chemo- and Site-Selective Nitrene Transfer Reactions through the Rational Design of Silver(I) Catalysts

Abstract: ConspectusCarbon–nitrogen (C–N) bonds are ubiquitous in pharmaceuticals, agrochemicals, diverse bioactive natural products, and ligands for transition metal catalysts. An effective strategy for introducing a new C–N bond into a molecule is through transition metal-catalyzed nitrene transfer chemistry. In these reactions, a metal–supported nitrene can either add across a C═C bond to form an aziridine or insert into a C–H bond to furnish the corresponding amine. Typical catalysts for nitrene transfer include Rh2Ln and Ru2Ln complexes supported by bridging carboxylate and related ligands, as well as complexes based on Cu, Co, Ir, Fe, and Mn supported by porphyrins and related ligands.A limitation of metal-catalyzed nitrene transfer is the ability to predictably select which specific site will undergo amination in the presence of multiple reactive groups; thus, many reactions rely primarily on substrate control. Achieving true catalyst-control over nitrene transfer would open up exciting possibilities for fle...

Arylation of halogenated pyrimidines via a Suzuki coupling reaction.

Abstract: The Suzuki coupling reaction has been used extensively for the synthesis of a wide variety of unsymmetrical biaryl compounds. We have extended this reaction to demonstrate the utility of preparing monophenyl-, diphenyl-, or triphenylpyrimidine depending on the reaction conditions. Further, it has been shown that chloropyrimidine substrates are preferable over iodo-, bromo-, or fluoropyrimidines.

Mechanistic Aspects and Synthetic Applications of Radical Additions to Allenes.

Abstract: More than 50 years have passed since Haszeldine reported the first addition of a trifluoromethyl radical to an allene; in the intervening years, both the chemistry of allenes and the reactivity of single-electron species have become topics of intense interest. In this Review, we provide an overview of the fundamentals of radical additions to allenes and highlight the emergence of theoretical and experimental evidence that reveals unique reactivity patterns for radical additions to allenes as compared with other unsaturated compounds. Factors capable of exerting control over the chemo-, regio-, and stereoselectivities of the attack of carbon- and heteroatom-based radicals at each of the three potential reactive sites in an allene substrate are described. These include reaction conditions, the nature of the attacking radical, the substitution pattern of the allene, and the length of the linker between the radical center and the proximal allene carbon in the substrate. Cycloaddition reactions between allenes and partners containing π-bonds, which are likely to proceed through radical pathways, are presented to highlight their ability to rapidly access complex polycyclic scaffolds. Finally, the synthetic utility of the products arising from these chemistries is described, including their applications to the construction of complex molecules.

Catalyst-Controlled and Tunable, Chemoselective Silver-Catalyzed Intermolecular Nitrene Transfer: Experimental and Computational Studies

Abstract: The development of new catalysts for selective nitrene transfer is a continuing area of interest. In particular, the ability to control the chemoselectivity of intermolecular reactions in the presence of multiple reactive sites has been a long-standing challenge in the field. In this paper, we demonstrate examples of silver-catalyzed, nondirected, intermolecular nitrene transfer reactions that are both chemoselective and flexible for aziridination or C–H insertion, depending on the choice of ligand. Experimental probes present a puzzling picture of the mechanistic details of the pathways mediated by [(tBu3tpy)AgOTf]2 and (tpa)AgOTf. Computational studies elucidate these subtleties and provide guidance for the future development of new catalysts exhibiting improved tunability in group transfer reactions.

Ligand-Controlled, Tunable Silver-Catalyzed C–H Amination

Abstract: The development of readily tunable and regioselective C–H functionalization reactions that operate solely through catalyst control remains a challenge in modern organic synthesis. Herein, we report that simple silver catalysts supported by common nitrogenated ligands can be used to tune a nitrene transfer reaction between two different types of C–H bonds. The results reported herein represent the first example of ligand-controlled and site-selective silver-promoted C–H amination.

Hydroamination: direct addition of amines to alkenes and alkynes.

Abstract: 8.4.5. Nitromercuration Reactions 3878 9. Hydroamination of Alkenes and Alkynes under Microwave Irradiation 3878 * To whom correspondence should be addressed. Phone: +49 241 8

Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications

Abstract: Catalytic transformation of ubiquitous C–H bonds into valuable C–N bonds offers an efficient synthetic approach to construct N-functionalized molecules. Over the last few decades, transition metal catalysis has been repeatedly proven to be a powerful tool for the direct conversion of cheap hydrocarbons to synthetically versatile amino-containing compounds. This Review comprehensively highlights recent advances in intra- and intermolecular C–H amination reactions utilizing late transition metal-based catalysts. Initial discovery, mechanistic study, and additional applications were categorized on the basis of the mechanistic scaffolds and types of reactions. Reactivity and selectivity of novel systems are discussed in three sections, with each being defined by a proposed working mode.

Synthesis and Applications of tert-Butanesulfinamide

Abstract: 10.2. Synthesis of Other -Amino Acid Derivatives 3676 10.2.1. Synthesis of -Amino Ketones 3676 10.2.2. Synthesis of -Amino Nitriles 3679 10.2.3. Synthesis of -Amino Phosphinates 3680 10.2.4. Synthesis of -Amino Sulfonates 3681 11. Synthesis of 1,2-Amino Alcohols 3681 11.1. 1,2-Addition to R-Alkoxy Imines 3681 11.2. 1,2-Addition of R-Substituted Organometallic Reagents to N-tert-Butanesulfinyl Imines 3687 * E-mail: jellman@berkeley.edu. † These authors contributed equally to this work. Chem. Rev. 2010, 110, 3600–3740 3600