A Tandem Approach to Functionalized Carbazoles from Indoles via Two Successive Regioselective Oxidative Heck Reactions Followed by Thermal Electrocyclization. -The synthesis of functionalized carbazoles is achieved via two successive oxidative Heck-reactions, subsequent 6-electrocyclization, and oxidative aromatization. The synthesis of unsymmetrically and trisubstituted carbazoles (XI) and (XIII) is also presented. -(LAHA*, J. K.; DAYAL, N.; Org. Lett. 17 (2015) 19, 4742-4745,

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The formation of ordered dolomite under Earth's surface conditions remains a challenge, although many researchers have now shown that microbes can facilitate the precipitation of this common mineral. This study provides the first evidence of dolomite biomineralization by the green alga Spirogyra (Zygnematales, Chlorophyta), a globally dispersed lacustrine genus. Microbial mats formed by Spirogyra occur in the hyperalkaline and ephemeral lake Caballo Alba, located in Central Spain and characterized by water solutions with high Mg/Ca ratios. Microscopic, geochemical, mineralogical and cytochemical studies have shown that accumulations of carbonates occur within different cells and locations of the alga. Biominerals mostly consist of single crystals of magnesian calcite and dolomite with variable proportions of Ca 2+ and Mg 2+ . High-resolution transmission electron microscopy and selected area electron diffraction patterns of the carbonates confirm the pervasive presence of super-lattice reflections typical of ordered dolomite in compositions with greater than 32 mol% MgCO 3 . The curved surfaces of some carbonate crystals and their attachment to the organic surfaces represent imprints of a confined growth in compartments that act as a template for crystal nucleation and shape the crystals. Dyes reveal chemical differences in these compartments which explain the polymineral biomineralization and suggest that the alga do not strictly control the precipitation process. Zygnematales algae related with Spirogyra date back possibly to the Early Palaeozoic, thus suggesting that dolomite biomineralization could have been a common process through the Phanerozoic. This discovery provides new insight into the biotic formation of orderly dolomite and aids in the reconstructions of past lacustrine environments of dolomite deposition.

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