The discovery of catalytic systems based on earth-abundant transition metals for the functionalization of C–H bonds enables streamlined and sustainable solutions to problems in synthetic organic chemistry. In this Communication, we disclose an iron-based catalytic system for the functionalization of propargylic and allylic C–H bonds. Inexpensive and readily available cyclopenta­dienyliron­(II) dicarbonyl complexes were employed as catalysts for a novel deprotonative activation mode for C–H functionalization, an approach that allows for the direct union of unsaturated building blocks with aryl aldehydes and other carbonyl electrophiles to deliver a range of unsaturated alcohol coupling products under operationally simple and functional group tolerant reaction conditions.

The reactions involved in the industrial production of epichlorohydrin from dichloropropanols (DCP, including 1,3-dichloro-2-propanol and 2-3-dichloro-1-propanlol) have been kinetically investigated. The kinetics of dehydrochlorination of DCP has been studied in the presence of caustic soda, by potentiometric techniques. The kinetic parameters of the reactions have been determined. The epichlorohydrin hydrolysis has been studied by measuring the decrease of the reagents during the time using titration. The whole study indicate that both dehydrochlorination and hydrolysis reaction can be considered as second order kinetic reaction. It is also indicated that the kinetic constant for dehydrochlorination reaction is far bigger than that for hydrolysis reaction in the same conditions.

Two total syntheses of the unsymmetrical bis-indolylquinone natural product demethylasterriquinone B1 (also known as L-783,281) have been accomplished. The first exploits a known base-promoted condensation of indoles with bromanil, which stops at monoaddition using the sterically hindered 2-isoprenylindole. This permits addition of the second indole, 7-prenylindole, which gives both meta- and para-substituted bis-indolylquinone products. This regiochemical control problem was solved by extension of a method we recently developed for acid-promoted addition of indoles to 2,5-dichlorobenzoquinone. Under our original mineral acid conditions, reaction of 2-isoprenylindole with dichlorobenzoquinone fails, but it succeeds with 3-bromo-2,5-dichlorobenzoquinone using acetic acid as the promoter. The regiochemistry established in such selectively bromine-substituted quinones can be exploited in Stille couplings. As a model system, the synthesis of demethylasterriquinone A1 was accomplished using as the key step a Stille coupling of a 2,5-dibromobenzoquinone with an (N-isoprenylindol-3-yl)tin, producing the para-substituted bis-indolylquinone exclusively. Use of a (7-prenylindole)tin in coupling with a bromo-2,5-dichloro-4-indolylbenzoquinone gives the demethylasterriquinone B1 precursor. The dihaloquinone products of these indole/quinone coupling processes can be hydrolyzed to the dihydroxyquinone natural products. Demethylasterriquinone B1 is of high recent interest as a small molecule insulin mimetic with oral anti-diabetic activity in mice.

The deprotonation of propargylic C–H bonds for subsequent functionalization typically requires stoichiometric metal alkyl or amide reagents. In addition to the undesirable generation of stoichiometric metallic waste, these conditions limit...