A 1,2,3,4-tetrahydro[60]fullerene with a five-membered heterocycle fused to a [5,6] junction was obtained with high regioselectivity by electrochemical functionalization of a [60]fulleroindoline. The structure was determined by spectroscopic data. A plausible reaction mechanism supported by computational calculations is proposed.

Fullerene derivatives with different addition patterns exhibit different physical, chemical, and biological properties, which are important for fullerene applications. Novel and rare 1,2,3,16-functionalized [60]fullerene derivatives having a five-membered heterocycle fused to a [5,6]-junction were obtained with high regioselectivity by electrochemical derivatization of a [60]fulleroindoline. The product structures were determined by spectroscopic data and single-crystal X-ray analysis. The obtained high regioselectivity was rationalized using theoretical calculations.

A highly efficient, air- and moisture-stable and easily recoverable magnetic nanoparticle-supported palladium catalyst has been developed for the Suzuki, Sonogashira and Heck reactions. A wide range of substrates was coupled successfully under aerobic conditions. In particular, the performance of the magnetic separation of the catalyst was very efficient, and it is possible to recover and reuse it at least eight times without significant loss of its catalytic activity.

The apparently simple Michael reaction of dimedone with chalcones afforded three types of products. The reaction of dimedone with chalcones in water at reflux, mediated by cetyltrimethylammonium bromide, gave the expected Michael adducts in good to excellent yields after purification by column chromatography. The attempted purification of the Michael adducts by recrystallization from ethanol in air unexpectedly generated hydroperoxidated and hydroxylated Michael adducts in low yields. The efficient synthesis of hydroperoxidated Michael adducts could be achieved in nearly quantitative yields by autoxidation of the Michael adducts in 1,2-dichloroethane at room temperature under aerobic conditions. The conversion of the hydroperoxidated Michael adducts to hydroxylated Michael adducts was facilitated by reduction with triphenylphosphane in excellent yields. Some of the reported Michael adducts in the literature need to be reassigned. Particular caution must be exerted to assign the Michael products generated from cyclic β-diketones, such as dimedone, because different purification processes may give different types of products.

The reaction of C₇₀ with CH₂(PO₃Et₂)₂ or CH₂(PO₃Et₂)CN in the presence of NaH has been reinvestigated. The reaction of C₇₀ with the former phosphonate affords five products. Products 1–3 have molecular structures C₇₀>CH(PO₃Et₂), whereas products 4 and 5 have molecular structures C₇₀>C(PO₃Et₂)₂. In contrast, only one product 6, with a molecular structure C₇₀>C(PO₃Et₂)CN, could be isolated from the reaction of C₇₀ with CH₂(PO₃Et₂)CN and NaH. Ultrasonication was used to shorten the reaction times and increase the product yields. No product resulting from addition to the C7–C21 bond of C₇₀ was observed in either cycloaddition reaction. Accordingly, the previously reported major products 3 and 6, which were assigned as the C7–C21 isomers, should be reassigned as the C1–C2 isomers. This correction is very important for understanding the reactivity of C₇₀. Our reassignments are further supported by theoretical calculations. The newly isolated minor products 1, 2, and 4 were identified as the C5–C6 isomers. The present work proves that the reactivity order of the bonds in C₇₀ for these two reactions is C1–C2 > C5–C6. These results resolve the confusion caused by previous incorrect product assignments.

Merrifield resin-supported pyrrolidine-based chiral organocatalysts A−D through A³-coupling reaction linkage have been developed and found to be highly effective catalysts for the Michael addition reaction of ketones with nitrostyrenes. The reactions generated the corresponding products in good yields (up to 92%), excellent enantioselectivities (up to 98% ee), and high diastereoselectivities (up to 99:1 dr). In addition, the catalysts can be reused at least five times without a significant loss of catalytic activity and stereoselectivity. Chirality, 2010. © 2009 Wiley-Liss, Inc.

The endohedral ¹H NMR chemical shifts of various known H₂- H₂O- and NH₃-encapsulated fullerene compounds have been calculated at the GIAO-B3LYP/3-21G and GIAO-HF/3-21G levels of theory with AM1- and PM3-optimized structures. The corrected ¹H NMR chemical shifts were calculated from the correlation equation derived from linear regression fitting between calculated and experimental ¹H NMR chemical shifts in each case. Comparisons of the regression coefficients, standard deviations, and maximum and mean errors of the corrected chemical shifts obtained by the four methods employed showed that the GIAO-B3LYP/3-21G//PM3 method is the best for calculating the endohedral ¹H NMR chemical shifts of endofullerenes. The endohedral ¹H NMR chemical shifts of any H₂-, H₂O- or NH₃-encapsulated fullerene compound can be predicted by the correlation equation derived by using the GIAO-B3LYP/3-21G//PM3 method. The shift tendency of endohedral ¹H NMR chemical shifts are discussed and compared with that of endohedral ³He NMR chemical shifts. The encapsulated H₂, H₂O or NH₃ molecule can be employed as a sensitive NMR probe to investigate the ring currents of fullerene cages and to follow the chemical reactions of endofullerenes at the exterior of the fullerene cage.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

12-Phosphotungstic acid was used as an efficient, ecofriendly, and air- and moisture-stable catalyst to promote the direct substitution of the hydroxy group of benzylic and allylic alcohols with various β-dicarbonyl compounds. This powerful protocol for carbon–carbon bond-forming reactions provides monoalkylated dicarbonyl compounds in high yields with great efficiency.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

An efficient and practical procedure for the aminohalogenation of electron-deficient olefins promoted by hypervalent iodine compounds has been demonstrated. The catalytic efficiency of various hypervalent iodine compounds with different carboxylic and sulfonic ligands has also been investigated and of these (diacetoxyiodo)benzene exhibited the highest activity. A series of substrates, including α,β-unsaturated ketones, cinnamates, and cinnamides, were tolerable under the conditions employed and were aminochlorinated/-brominated in good yields and with excellent diastereoselectivities.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Mild nucleophilic substitution reactions of benzhydrylic, benzylic, allylic, and simple aliphatic alcohols with sulfonamides, benzamide, and 4-nitroaniline in the presence of 12-phosphotungstic acid as an efficient, eco-friendly, cheap, and air- and moisture-tolerant catalyst for the construction of C–N bonds has been investigated. The amine derivatives were obtained in good yields (up to 98 %). The reusable nature of the 12-phosphotungstic acid makes this protocol more attractive.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)