Iron-Catalyzed Divergent Tandem Radical Annulation of Aldehydes with Olefins toward Indolines and Dihydropyrans.

Iron-catalyzed divergent tandem radical annulations of aldehydes with olefins are reported. The new strategy allows the rapid and efficient construction of various multifunctionlized indolines (R = Ar) and dihydropyrans (R = Me), which are significant skeletons in bioactive natural products and pharmaceuticals. The substituents of tertiary amines play vital roles to facilitate the desired transformation. Mechanistic studies on indoline formation disclose that the homolytic cleavage of the carbonyl C-H bond might be involved in the rate-determining step, while dissociation of the aromatic C-H bond was most likely included in the product-determining step.

Iron-catalyzed acylation-oxygenation of terminal alkenes for the synthesis of dihydrofurans bearing a quaternary carbon.

Iron-catalyzed acylation-oxygenation of terminal alkenes is reported. Acyl radicals generated by the oxidation of aldehydes add to terminal alkenes and followed by intramolecular oxygenation give functionalized 2,3-dihydrofuran derivatives bearing a quaternary carbon.

Synthesis and characterization of multi-active site grafting starch copolymer initiated by KMnO4 and HIO4/H2SO4 systems.

A novel initiator system containing KMO4, HIO4, and H2SO4 for synthesizing grafting starch copolymers is reported. In this system, KMnO4 was used to oxidize the primary hydroxyl group to aldehyde group of glucose in the starch, and the formed aldehyde group reacted with Mn(4+), Mn(3+) to afford starch free radical. At the same time HIO4 perform as the oxidant to open the C2C3 bond of glucose ring in starch to form two more aldehyde groups, and then two more free radicals are generated. As a result one glucose unit could provide ultimately three active sites for starch grafting reaction. Graft copolymers with a higher grafting ratio and grafting efficiency could be obtained by using the composite initiation system than the KMnO4/H2SO4 initiation system. The grafting of polyacrylamide onto the corn starch backbone was confirmed by viscometry, elemental analysis, infrared spectroscopy, nuclear magnetic resonance, X-ray diffraction and scanning electron microscopy.

Unstable-Fe-site-induced formation of mesopores in microporous zeolite Y without using organic templates.

A novel organic template-free strategy for generating mesoporosity in Y zeolites is reported. It is revealed that Fe(3+) functioned as unstable sites in the Fe-NaY zeolite, which promotes deferrization-dealumination, leading to enhanced formation of intra-crystalline mesopores as well as desirable interconnectivity. The mesopore-enriched zeolite exhibits a remarkable ability in conversion of the bulky substrate.

Direct benzothiophene formation via oxygen-triggered intermolecular cyclization of thiophenols and alkynes assisted by manganese/PhCOOH.

An intermolecular oxidative cyclization between thiophenols and alkynes for benzothiophene formation has been established. A variety of multifunctional benzothiophenes are synthesized. In addition, we demonstrated that the obtained benzothiophenes can be used for further transformation to give diverse benzothiophene derivatives efficiently and selectively.

Zirconium-mediated selective synthesis of 1,2,4,5-tetrasubstituted benzenes from two silyl-substituted alkynes and one internal alkyne.

Selective synthesis of 1,2,4,5-tetrasubstituted benzenes was achieved via formation of 2,5-bis(trimethylsilyl)zirconacyclopentadienes from 2 equiv of TMS-substituted alkynes with Cp(2)ZrBu(2) and Cu-mediated formation of 1,4-disilylbenzene by cycloaddition of zirconacyclopentadienes to disubstituted alkynes. Preparation of 1,2,3,4,9,10-hexasubstituted pentacene and 2,3,6,11-tetrasubstituted naphthacene derivatives were demonstrated by a homologation or coupling method using tetrasubstituted benzene.