1,3-Dipolar cycloadditions of azomethine imines

Azomethine imines are considered 1,3-dipoles of the aza-allyl type which are transient intermediates and should be generated in situ but can also be stable and isolable compounds. They react with electron-rich and electron-poor olefins as well as with acetylenic compounds and allenoates mainly by a [3 + 2] cycloaddition but they can also take part in [3 + 3], [4 + 3], [3 + 2 + 2] and [5 + 3] with different dipolarophiles. These 1,3-dipolar cycloadditions (1,3-DC) can be performed not only under thermal or microwave conditions but also using metallo- and organocatalytic systems. In recent years enantiocatalyzed 1,3-dipolar cycloadditions have been extensively considered and applied to the synthesis of a great variety of dinitrogenated heterocycles with biological activity. Acyclic azomethine imines derived from mono and disubstituted hydrazones could be generated by prototropy under heating or by using Lewis or Brønsted acids to give, after [3 + 2] cycloadditions, pyrazolidines and pyrazolines. Cyclic azomethine imines, incorporating a C–N bond in a ring, such as isoquinolinium imides are the most widely used dipoles in normal and inverse-electron demand 1,3-DC allowing the synthesis of tetrahydro-, dihydro- and unsaturated pyrazolo[1,5-a]isoquinolines in racemic and enantioenriched forms with interesting biological activity. Pyridinium and quinolinium imides give the corresponding pyrazolopyridines and indazolo[3,2-a]isoquinolines, respectively. In the case of cyclic azomethine imines with an N–N bond incorporated into a ring, N-alkylidene-3-oxo-pyrazolidinium ylides are the most popular stable and isolated dipoles able to form dinitrogen-fused saturated and unsaturated pyrazolopyrazolones as racemic or enantiomerically enriched compounds present in many pharmaceuticals, agrochemicals and other useful chemicals.

Regio and diastereoselective multicomponent 1,3-dipolar cycloadditions between prolinate hydrochlorides, aldehydes and dipolarophiles for the direct synthesis of pyrrolizidines

A general synthesis of highly substituted pyrrolizidines can be performed by a multicomponent 1,3-dipolar cycloaddition using proline ester hydrochlorides, aldehydes and dipolarophiles, at room temperature without catalysts or in the presence of AgOAc (5 mol %). In the case of (2S,4R)-4-hydroxyproline derivatives it is possible to obtain enantioenriched pyrrolizidines with high control of the regio- and diastereoselectivity affording the adducts 2,4-trans-2,5-trans according to an endo-approach and a S-dipole geometry of the in situ generated azomethine ylide. For proline esters a similar regioselectivity and endo-diastereoselectivity are observed when the dipole promotes an α-attack. However, when ethyl glyoxylate is used as aldehyde component the γ-attack of the S-ylide takes place preferentially giving rise the opposite regioselectivity for acrylic dipolarophiles, being crucial the role of silver acetate. In this case, the exo-adducts with a 2,3-cis-2,5-trans relative configuration are diastereoselectively obtained. In addition, computational studies have also been carried out to shed light on the origins of the diastereo- and regioselectivity observed for the described 1,3-dipolar cycloadditions.

Organocatalytic Asymmetric α-Chlorination of 1,3-Dicarbonyl Compounds Catalyzed by 2-Aminobenzimidazole Derivatives

Bifunctional chiral 2-aminobenzimidazole derivatives 1 and 2 catalyze the enantioselective stereodivergent α-chlorination of β-ketoesters and 1,3-diketone derivatives with up to 50% ee using N-chlorosuccinimide (NCS) or 2,3,4,4,5,6-hexachloro-2,5-cyclohexadien-1-one as electrophilic chlorine sources.

Meeting minutes maintained by the Secretary, April 21, 1812; May 4, 1812; and June 3, 1812

These minutes pertain to discussions of the General Court's "act to repeal an act" (also called "the Act to alter and amend the Constitution of the Board of Overseers of Harvard College, and to regulate certain meetings of said Board") in February 1812, which repealed changes made in 1810 to the Constitution of the Board of Overseers. The Overseers present at these meetings doubted the act's legality and discussed ignoring and/or attempting to overturn the act.

(Tables 1-3) Amphipod species observed under Antarctic pack ice during POLARSTERN cruises ANT-XXI/4, ANT-XXII/2 and ANT-XXIII/6

During three Antarctic expeditions (2004, ANT XXI-4 and XXII-2; 2006, ANT XXIII-6) with the German research icebreaker R/V Polarstern, six different amphipod species were recorded under the pack ice of the Weddell Sea and the Lazarev Sea. These cruises covered Austral autumn (April), summer (December) and winter (August) situations, respectively. Five of the amphipod species recorded here belong to the family Eusiridae (Eusirus antarcticus, E. laticarpus, E. microps, E. perdentatus and E. tridentatus), while the last belongs to the Lysianassidea, genus Cheirimedon (cf. femoratus). Sampling was performed by a specially designed under-ice trawl in the Lazarev Sea, whereas in the Weddell Sea sampling was done by scuba divers and deployment of baited traps. In the Weddell Sea, individuals of E. antarcticus and E. tridentatus were repeatedly observed in situ during under-ice dives, and single individuals were even found in the infiltration layer. Also in aquarium observations, individuals of E. antarcticus and E. tridentatus attached themselves readily to sea ice. Feeding experiments on E. antarcticus and E. tridentatus indicated a carnivorous diet. Individuals of the Lysianassoid Cheirimedon were only collected in baited traps there. Repeated conventional zooplankton hauls performed in parallel to this study did not record any of these amphipods from the water column. In the Lazarev Sea, E. microps, E. perdentatus and E. laticarpus were regularly found in under-ice trawls. We discuss the origin and possible sympagic life style of these amphipods.

Consent decree program of the Department of Justice : Hearings before the Antitrust Subcommittee (Subcommittee no. 5) ... Pt. II, vol. 1-3 American telephone & telegraph co.

Mode of access: Internet.

Biographical directory of the American Congress, 1774-1961 : the Continental Congress, September 5, 1774, to October 21, 1788 and the Congress of the United States, from the First to the Eighty-sixth Congress, March 4, 1789, to January 3, 1961, inclusive.

"This volume, compiled by Clifford P. Reynolds, publications technician of the [Joint] Committee [on Printing], is a revision of the Dictionary of the United States Congress and the general government, published in 1859 and again revised in 1869, by Charles Lanman; the Biographical annals of the civil government of the United States in 1876, by Joseph Lanman and James Anglin, and the Lanman edition of 1876 as corrected by Joseph M. Morrison in 1887; the Political register and congressional directory of 1878; by Ben: Perley Poore; the Biographical congressional directory of 1903, by O. M. Enyart; the Biographical congressional directory in 1911, the Biographical directory of the American Congress of 1927, by Ansel Wold, and the 1949 edition by James L. Harrison."