Informing The Legislature

Pennsylvania, similar to many other states, has faced a tremendous shift of legislative make-up in recent years from rural to urban representation

Chairman's Address at the Joint Meeting of the National Dental Association and the Interstate Association of Anesthetists at Louisville, KY., July 27, 1916

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Space weather effects on drilling accuracy in the North Sea

The oil industry uses geomagnetic field information to aid directional drilling operations when drilling for oil and gas offshore. These operations involve continuous monitoring of the azimuth and inclination of the well path to ensure the target is reached and, for safety reasons, to avoid collisions with existing wells. Although the most accurate method of achieving this is through a gyroscopic survey, this can be time consuming and expensive. An alternative method is a magnetic survey, where measurements while drilling (MWD) are made along the well by magnetometers housed in a tool within the drill string. These MWD magnetic surveys require estimates of the Earth’s magnetic field at the drilling location to correct the downhole magnetometer readings. The most accurate corrections are obtained if all sources of the Earth’s magnetic field are considered. Estimates of the main field generated in the core and the local crustal field can be obtained using mathematical models derived from suitable data sets. In order to quantify the external field, an analysis of UK observatory data from 1983 to 2004 has been carried out. By accounting for the external field, the directional error associated with estimated field values at a mid-latitude oil well (55 N) in the North Sea is shown to be reduced by the order of 20%. This improvement varies with latitude, local time, season and phase of the geomagnetic activity cycle. By accounting for all sources of the field, using a technique called Interpolation In-Field Referencing (IIFR), directional drillers have access to data from a “virtual” magnetic observatory at the drill site. This leads to an error reduction in positional accuracy that is close to matching that of the gyroscopic survey method and provides a valuable independent technique for quality control purposes

Organocatalytic Vinyl and Friedel−Crafts Alkylations with Trifluoroborate Salts

Herein we report the first use of vinyl and heteroaryl trifluoroborate salts as viable substrates for amine-catalyzed conjugate additions. The application of LUMO-lowering iminium catalysis has enabled the highly regio- and enantioselective 1,4-addition of rationally designed trifluoroborate salt nucleophiles to α,β-unsaturated aldehydes. Imidazolidinone 2•HCl was found to catalyze the addition of various BF_3K-derived heteroaryl and vinyl species to a range of enals with excellent levels of enantioselectivity. Importantly, the use of these salts can enable nontraditional regiocontrol as part of a Friedel−Crafts pathway. Boronic acids can also be employed as viable π-nucleophiles for these asymmetric conjugate additions provided that in situ activation to the corresponding boronate species is accomplished. While BF_3K salts are routinely employed in transition metal catalysis, to our knowledge, this is the first use of this activation group for organic catalysis or Friedel−Crafts alkylations

Editor\u27s Corner

From the Outgoing Managing Editor: The start of 1985 signals the transfer of the last vestiges of my former position as executive director of the Academy to Jim Macmillan, who now takes on the role of managing editor of Academy publications

Development of a New Lewis Acid-Catalyzed [3,3]-Sigmatropic Rearrangement: The Allenoate-Claisen Rearrangement

A new Lewis acid-catalyzed Claisen rearrangement has been developed that allows the stereoselective construction of β-amino-α,β,ε,ζ-unsaturated-γ,δ-disubstituted esters from simple allylic amines and allenoate esters. This reaction, which is contingent upon the use of Lewis acid, can be conducted with a range of metal salts (Yb(OTf)_3, AlCl_3, Sn(OTf)_2, Cu(OTf)_2, MgBr_2·Et_2O, FeCl_3, Zn(OTf)2) with catalyst loadings as low as 5 mol %. This catalytic process provides access to a diverse range of β-amino-α,β,ε,ζ-unsaturated-γ,δ-disubstituted esters in high yield and with excellent levels of diastereoselectivity for a series of allyl pyrrolidines (R_1 = H, Me, i-Pr, Ph, NR_2 = pyrrolidine, piperidine, Nme_2; ≥81% yield, ≥94:6 syn:anti) and allenoate esters (R_2 = H, Me, i-Pr, Ph, allyl, NPht, Cl; ≥75% yield, ≥91:9 syn:anti). The capacity of this new Claisen rearrangement to provide catalytic access to elusive structural motifs has also been demonstrated in the stereospecific formation of quaternary carbon bearing frameworks arising from geranyl- and neryl pyrrolidine (≥93% yield, >98:2 dr)

Enantioselective Organocatalytic Cyclopropanations. The Identification of a New Class of Iminium Catalyst Based upon Directed Electrostatic Activation

A new method for enantioselective organocatalytic cyclopropanation is described. This study outlines the identification of a new class of iminium catalyst based on the concept of directed electrostatic activation (DEA). This novel organocatalytic mechanism exploits dual activation of ylide and enal substrates through a proposed electrostatic activation and stereodirected protocol. Formation of trisubstituted cyclopropanes with high levels of enantio- and diastereoinduction is accomplished for a variety of α,β-unsaturated aldehydes and sulfonium ylides. In addition, mechanistic studies have found that this cyclopropanation reaction exhibits enantioselectivity and reactivity profiles that are in accord with the proposed DEA step

The First Direct and Enantioselective Cross-Aldol Reaction of Aldehydes

The first enantioselective catalytic direct cross-aldol reaction that employs nonequivalent aldehydes has been accomplished using proline as the reaction catalyst. Structural variation in both the aldol donor (R_1 = Me, n-Bu, Bn, 91 to >99%) and aldol acceptor (R_2 = I-Pr, I-Bu, c-C6H11, Et, Ph, 97−99% ee) are possible while maintaining high reaction efficiency (75−88% yield). Significantly, this new aldol variant allows facile enantioselective access to a broad range of β-hydroxy aldehydes which are valuable intermediates in polyketide syntheses

Enantioselective Organocatalytic Indole Alkylations. Design of a New and Highly Effective Chiral Amine for Iminium Catalysis

The indole framework has become widely identified as a “privileged” structure with representation in over 3000 natural isolates and 40 medicinal agents of diverse therapeutic action. A new strategy for asymmetric access to this important pharmacaphore has been accomplished that involves the amine catalyzed alkylation of indoles with α,β-unsaturated aldehydes. Central to these studies has been the design of a new chiral amine catalyst that exhibits improved reactivity and selectivity for iminium catalysis. This new (2S,5S)-5-benzyl-2-tert-butyl-imidazolidinone catalyst has enabled the conjugate addition of a variety of indole systems to a diverse range of α,β-unsaturated aldehydes in high yield and with excellent levels of enantiocontrol (70−97% yield, 84−97% ee). A demonstration of the utility of this new organocatalytic alkylation for the rapid construction of biomedically relevant molecules is presented in the enantioselective synthesis of an indolobutyric acid COX-2 inhibitor