Development of a tandem cyclization mediated by samarium(II) iodide: sequential intramolecular conjugate addition/nucleophilic acyl substitution

The development of a one-pot tandem intramolecular conjugate addition/nucleophilic acyl substitution using samarium(II) iodide is reported. The reaction relies on the reagent’s unique ability to mediate both radical and anionic pathways, which are likely integral to the mechanism of this transformation. The tricyclic hemiacetal product was formed in good yield, with excellent diastereoselectivity, and its structure was verified by X-ray crystallographic analysis.     

Highly efficient nickel-catalyzed cross-coupling of succinic and glutaric anhydrides with organozinc reagents

A nickel-catalyzed alkylation of succinic and glutaric anhydrides with alkyl- and arylzinc reagents has been developed. A dramatic olefin effect has been investigated resulting in the identification of several styrene-based promoters which show pronounced enhancements in reaction rate. The substrate scope with respect to electrophilic and nucleophilic coupling partners has been examined and found to be remarkably broad, allowing for rapid introduction of molecular complexity through the use of functionalized coupling partners. Regioselective alkylation of an unsymmetrical succinic anhydride and a profound effect of pendent coordinating olefins on reaction rate suggest a mechanism involving discrete oxidative addition of the nickel complex into the cyclic anhydride followed by a transmetalation event.     

Critical reflexivity in financial markets: a Hawkes process analysis

We model the arrival of mid-price changes in the E-mini S&P futures contract as a self-exciting Hawkes process. Using several estimation methods, we find that the Hawkes kernel is power-law with a decay exponent close to ?1.15 at short times, less than ≈ 10³ s, and crosses over to a second power-law regime with a larger decay exponent ≈–1.45 for longer times scales in the range [10³ ,10⁶ ] seconds. More importantly, we find that the Hawkes kernel integrates to unity independently of the analysed period, from 1998 to 2011. This suggests that markets are and have always been close to criticality, challenging a recent study which indicates that reflexivity (endogeneity) has increased in recent years as a result of increased automation of trading. However, we note that the scale over which market events are correlated has decreased steadily over time with the emergence of higher frequency trading.     

Diastereoselective palladium-catalyzed alpha-arylation of 4-substituted cyclohexyl esters

A diastereoselective palladium-catalyzed arylation of 4-substituted cyclohexyl esters has been developed. The reaction proceeds at room temperature in the presence of [(t-Bu3P)PdBr]2 providing products in up to 37:1 dr.