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Unified Structural Representation of the southern California crust and upper mantle
We present a new, 3D description of crust and upper mantle velocity structure in southern California implemented as a Unified Structural Representation (USR). The USR is comprised of detailed basin velocity descriptions that are based on tens of thousands of direct velocity (Vp, Vs) measurements and incorporates the locations and displacement of major fault zones that influence basin structure. These basin descriptions were used to developed tomographic models of crust and upper mantle velocity and density structure, which were subsequently iterated and improved using 3D waveform adjoint tomography. A geotechnical layer (GTL) based on Vs30 measurements and consistent with the underlying velocity descriptions was also developed as an optional model component. The resulting model provides a detailed description of the structure of the southern California crust and upper mantle that reflects the complex tectonic history of the region. The crust thickens eastward as Moho depth varies from 10 to 40 km reflecting the transition from oceanic to continental crust. Deep sedimentary basins and underlying areas of thin crust reflect Neogene extensional tectonics overprinted by transpressional deformation and rapid sediment deposition since the late Pliocene. To illustrate the impact of this complex structure on strong ground motion forecasting, we simulate rupture of a proposed M 7.9 earthquake source in the Western Transverse Ranges. The results show distinct basin amplification and focusing of energy that reflects crustal structure described by the USR that is not captured by simpler velocity descriptions. We anticipate that the USR will be useful for a broad range of simulation and modeling efforts, including strong ground motion forecasting, dynamic rupture simulations, and fault system modeling. The USR is available through the Southern California Earthquake Center (SCEC) website (http://www.scec.org)
Synthesis of 2-Imidazolones and 2-Iminoimidazoles
Convenient methods for the direct conversion of imidazolium salts to the corresponding 2-imidazolone or 2-imino imidazole derivatives have been developed. Treatment of the salt with commercial bleach leads to effective oxidation at C2 and the formation of the corresponding imidazolone. Alternatively, treatment of the salt with an <i>N</i>-chloro amide affords the corresponding protected 2-amino derivative in good yield
Total Synthesis of 7′-Desmethylkealiiquinone
The total synthesis of an analogue of the marine alkaloid kealiiquinone has been completed through application of an intramolecular Diels–Alder reaction of an imidazole-containing enyne. Oxidative aromatization of the lactone adduct and <i>N</i>-methylation facilitates C2-oxidation via the imidazolium salt. Conversion of the lactone to the phthalaldehyde derivative and then to the dihydroxybenzoquinone was achieved via a reaction with glyoxal in the presence of KCN. Esterification of the vinylogous diacid and deprotection provided 7′-desmethylkealiiquinone
Total Synthesis of 7′-DesÂmethylÂkealiÂiquinone, 4′-DesÂmethoxyÂkealiÂiquinone, and 2‑DeoxyÂkealiÂiquinone
Synthetic
approaches to the imidazoÂnaphthoÂquinone core
of kealiiquinone and related <i>Leucetta</i>-derived alkaloids
are described. The polysubstituted benzimidazole framework can be
constructed through intramolecular Diels–Alder reactions of
propiolate-derived enynes followed by oxidation. Adjustment of the
oxidation state of the thus formed lactone allows introduction of
the 2,3-dihydroxyÂbenzoÂquinone moiety through a presumed
benzoin-like condensation between a phthaldehyde derivative and a
masked glyoxal equivalent catalyzed by a cyanide ion. Oxidation of
the C2-position can be accomplished through application of an operationally
simple treatment of an imidazolium salt with bleach, thus producing
the corresponding 2-imidazolone. Debenzylation of a late stage intermediate
en route to kealiiquinone was compromised by concomitant <i>O</i>-demethylation upon treatment with triflic acid resulting in the
formation of non-natural 7′-desÂmethylÂkealiÂiquinone.
Other endgame strategies were evaluated; however, these efforts did
not lead to completion of a synthesis of kealiiquinone but did provide
access to other closely related analogues