Applications of Boron in Iridium, Copper, and Nickel Catalysis; Synthesis and Design of Gene-Expression Dependent CO-Releasing Molecules

A method is reported for synthesis of synthetically-valuable borylated pyridines via a Lewis acid promoted C-H activation approach. The transformation involves BF3 or BH3 Lewis-acid precomplexation followed by Ir-catalyzed borylation. The method’s development was guided by computational studies, culminating in the development of a reaction with several advantages over existing methods, including enhanced reactivity, improved regioselectivity, novel formation of trifluoroborate salts and an operationally simple purification procedure. During the reaction discovery process, we also devised a convenient and rapid synthesis of isotopically enriched 10B-pinacolborane, which was used to probe the reaction mechanism. The synthesis and screening of various π-base ligands for use in a copper-promoted coupling reaction of alcohols and vinyl boronates are also highlighted. While alkenes and alkynes are frequently used as π–bond ligands in transition-metal promoted reactions, allenes have long been underutilized for this purpose despite possessing excellent π–bond donor characteristics. Several alkynes and allenes were synthesized and tested as π–bond ligands in a copper-mediated oxidative vinyl ether synthesis. Cyclonona-1,2-diene was identified as an ideal allene additive for the reaction. Next, building upon our previous work on palladium-catalyzed oxidative couplings of vinyl boronates, we describe our efforts towards translating this chemistry to a nickel-catalyzed manifold. Central to the success of this new method was the serendipitous discovery that nitroarenes act as a terminal oxidant for nickel, enabling the synthesis of biaryls and butadienes. To the best of our knowledge, this is the first example of nitroarenes used as oxidants in a nickel-catalyzed coupling reaction. The final part of this work chronicles the design and synthesis of a new class of carbon-monoxide releasing molecules. While carbon monoxide is a pervasive environmental toxin, it’s also an endogenously-produced, essential signaling molecule in all vertebrates. In order to better study the physiological effects of CO, we synthesized molecules which are activated by the presence of genetically programmable β-galactosidase enzyme. This chapter represents an important first step towards the realization of a useful biochemical tool and perhaps even a unique therapeutic compound

The Hebrew Bible as Mythic “Vocabulary”: Towards a New Comparative Mythology

In this article, I argue that the history of the study of myth in the Hebrew Bible has been, and continues to be, shaped in negative ways by an essentially Romantic Nationalist understanding of the relationship between a people and their traditions. I then argue that more appropriate ways of modeling the construction of the Bible’s myths, combined with new investigations into the historical development of biblical traditions themselves, reveals a surprising continuity between the myth-making activity of biblical authors and editors and that of all those who retell and adapt biblical traditions in extrabiblical materials. I conclude that the existence of large-scale continuities between the adaptation of biblical traditions in different periods allows for a new kind of comparative investigation. By studying the use of biblical traditions in biblical literature, extrabiblical literature, and art, on approximately equal terms, we can gain new insights about the construction of biblical myths themselves, while connecting the study of the Hebrew Bible far more closely to the study of other bodies of tradition, elsewhere and later on

A Different Path Taken: Texas Capital Offenders\u27 Post-Atkins Claims of Mental Retardation

In 2002, in Atkins v. Virginia, the United States Supreme Court held that the execution of mentally retarded offenders is unconstitutional, and entrusted the enforcement of this constitutional ban to the states. In the absence of legislative action in Texas, the Texas Court of Criminal Appeals has established substantive and procedural standards to resolve Texas offenders\u27 Atkins claims of mental retardation for offenders seeking state post-conviction relief. This Texas appellate court has also specified most of the standards to resolve Atkins claims at the trial court level and on direct appeal. The United States Court of Appeals for the Fifth Circuit has prescribed procedures for Texas capital offenders pursuing Atkins claims through federal collateral review, and has generally endorsed the Texas Atkins standards it has addressed. Since the Atkins ruling, ninety Texas capital offenders have had their Atkins claims resolved at the trial, appellate, or post-conviction levels-a volume of Atkins claimants that far exceeds that of any other capital punishment state. Texas Atkins claimants, however, have been meaningfully less successful than expert estimates of mental retardation among capital offenders would predict and than national estimates of success regarding Atkins claims have indicated. This Article examines the evolution of the Texas Atkins standards and their application to these ninety capital offenders. The Article then compares the implementation of Atkins in Texas to its implementation in other states, and addresses issues concerning Texas\u27s compliance with the Atkins mandate to identify mentally retarded offenders and exclude them from execution. The Article concludes with a discussion of potential responsive action concerning Texas\u27s Atkins implementation by the United States Supreme Court