Synthesis and late-stage functionalization of complex molecules through C-H fluorination and nucleophilic aromatic substitution.

We report the late-stage functionalization of multisubstituted pyridines and diazines at the position α to nitrogen. By this process, a series of functional groups and substituents bound to the ring through nitrogen, oxygen, sulfur, or carbon are installed. This functionalization is accomplished by a combination of fluorination and nucleophilic aromatic substitution of the installed fluoride. A diverse array of functionalities can be installed because of the mild reaction conditions revealed for nucleophilic aromatic substitutions (S(N)Ar) of the 2-fluoroheteroarenes. An evaluation of the rates for substitution versus the rates for competitive processes provides a framework for planning this functionalization sequence. This process is illustrated by the modification of a series of medicinally important compounds, as well as the increase in efficiency of synthesis of several existing pharmaceuticals

Costly and discrete communication: An experimental investigation

Language is an imperfect and uneven means of communicating information about a complex and nuanced world. We run an experimental investigation of a setting in which the messages available to the sender imperfectly describe the state of the world, however the sender can improve communication, at a cost, by increasing the complexity or elaborateness of the message. As is standard in the communication literature, the sender learns the state of the world then sends a message to the receiver. The receiver observes the message and provides a best guess about the state. The incentives of the players are aligned in the sense that both sender and receiver are paid an amount which is increasing in the accuracy of the receiver's guess. As would be expected, we find that larger communication costs are associated with worse outcomes for both sender and receiver. Consistent with the communication literature, albeit in very different setting, we find that there is overcommunication. For the receiver, there is a positive relationship between the payoffs relative to the equilibrium predictions and communication costs. This relationship is negative for the senders. We also find that the response time of both the sender and receiver are positively related to their payoffs.communication; cheap talk; overcommunication

Analysis of Screen Channel LAD Bubble Point Tests in Liquid Oxygen at Elevated Temperature

The purpose of this paper is to examine the key parameters that affect the bubble point pressure for screen channel Liquid Acquisition Devices in cryogenic liquid oxygen at elevated pressures and temperatures. An in depth analysis of the effect of varying temperature, pressure, and pressurization gas on bubble point is presented. Testing of a 200 x 1400 and 325 x 2300 Dutch Twill screen sample was conducted in the Cryogenics Components Lab 7 facility at the NASA Glenn Research Center in Cleveland, Ohio. Test conditions ranged from 92 to 130K and 0.138 - 1.79 MPa. Bubble point is shown to be a strong function of temperature with a secondary dependence on pressure. The pressure dependence is believed to be a function of the amount of evaporation and condensation occurring at the screen. Good agreement exists between data and theory for normally saturated liquid but the model generally under predicts the bubble point in subcooled liquid. Better correlation with the data is obtained by using the liquid temperature at the screen to determine surface tension of the fluid, as opposed to the bulk liquid temperature

Analysis of Screen Channel LAD Bubble Point Tests in Liquid Methane at Elevated Temperature

This paper examines the effect of varying the liquid temperature and pressure on the bubble point pressure for screen channel Liquid Acquisition Devices in cryogenic liquid methane using gaseous helium across a wide range of elevated pressures and temperatures. Testing of a 325 x 2300 Dutch Twill screen sample was conducted in the Cryogenic Components Lab 7 facility at the NASA Glenn Research Center in Cleveland, Ohio. Test conditions ranged from 105 to 160K and 0.0965 - 1.78 MPa. Bubble point is shown to be a strong function of the liquid temperature and a weak function of the amount of subcooling at the LAD screen. The model predicts well for saturated liquid but under predicts the subcooled data

Iridium-Catalyzed Silylation of Five-Membered Heteroarenes: High Sterically Derived Selectivity from a Pyridyl-Imidazoline Ligand.

The steric effects of substituents on five-membered rings are less pronounced than those on six-membered rings because of the difference in bond angles. Thus, the regioselectivities of reactions of five-membered heteroarenes that occur with selectivities dictated by steric effects, such as the borylation of C-H bonds, have been poor in many cases. We report that the silylation of five-membered-ring heteroarenes occurs with high sterically derived regioselectivity when catalyzed by the combination of [Ir(cod)(OMe)]2 (cod=1,5-cyclooctadiene) and a phenanthroline ligand or a new pyridyl-imidazoline ligand that further increases the regioselectivity. The silylation reactions with these catalysts produce high yields of heteroarylsilanes from functionalization at the most sterically accessible C-H bonds of these rings under conditions that the borylation of C-H bonds with previously reported catalysts formed mixtures of products or products that are unstable. The heteroarylsilane products undergo cross-coupling reactions and substitution reactions with ipso selectivity to generate heteroarenes that bear halogen, aryl, and perfluoroalkyl substituents