A palladium-catalyzed allylic alkylation of unsubstituted 2-cyanoacetates using a 1,1′-bi-2-naphthol-derived multifunctional N,O,P ligand is reported. A number of chiral monosubstituted 2-cyanoacetates with two adjacent stereogenic carbon centers are obtained in this Pd-catalyzed asymmetric allylic alkylation reaction, in which the multistereogenic and multifunctional 1,1′-bi-2-naphthol-derived N,O,P ligand-promoted Pd-catalyzed asymmetric allylic alkylation reaction proceeds smoothly in high diastereo- and enantioselectivity (up to >99:1 dr and up to 96 % ee).

A copper catalyst system derived from TaoPhos and CuF₂ was used successfully for catalytic asymmetric Huisgen [3+2] cycloaddition of azides and alkynes to give optically pure products containing succinimide- and triazole-substituted quaternary carbon stereogenic centers. The desired products were obtained in good yields (60–80 %) and 85:15 to >99:1 enantiomeric ratio (e.r.) in this click cycloaddition reaction.

In this work, we have developed a new approach to monodispersed hybrid Ag@TiO₂ nanocomposites using a titanium-promoted cross-linking reduction in the SiH functional material, polymethylhydrosiloxane (PMHS)-based semi-interpenetrating networks (PMHSIPN). The titania was designed to be highly dispersed on the functional material and then the Ag@TiO₂ nanoparticles were formed in uniform size and shape under mild conditions. The experimental results reveal that the nanosilver catalysts (the fabricated Ag@TiO₂ located on the PMHSIPNs, namely, nanoAg@TiO₂@PMHSIPN) have enhanced catalytic activities in the alkynylation of trifluoromethyl ketones or α,β-unsaturated trifluoromethyl ketones with terminal alkynes. In this reaction, the hybrid Ag@TiO₂ nanoparticles exhibited a high level of catalytic activity for the selective 1,2-alkynylation of various trifluoromethyl ketones and α,β-unsaturated trifluoromethyl ketones into a wide range of fluorinated alcohols in water. Finally, on the basis of the nanoAg@TiO₂@PMHSIPN-catalyzed alkynylation of trifluoromethyl ketones, we developed a new concept whereby highly reactive substrates act as a “reactive tractor” or “reactive springboard” to drive the transformation of poorly reactive substrates as springboard chemistry. Consequently, we found that trifluoromethyl ketone can be used as an efficient additive in the nanosilver-catalyzed alkynylation of aldehydes.

A series of silicon-containing diols are synthesized and used in lipase-catalyzed remote desymmetrization. This synthetic method is valuable in the construction of optically active silicon-stereogenic organosilicon compounds. Good enantioselectivities of the remote desymmetrization was achieved with Candida antarctica lipase B (CAL-B) (up to 90:10 er).

This minireview focuses on the recent advances in the synthetic application of amino acid-derived bifunctional phosphine catalysts bearing a hydrogen-bond donor. In the examples illustrated, the amino acid-based phosphines have already been proven to be versatile, catalyzing a wide range of asymmetric reactions, including (aza)-MBH reactions, [3+2] cyclizations, [4+2] cycloadditions, allylic alkylation, and Michael addition.

A highly efficient catalytic protocol for the isomerization of substituted amide-derived olefins is presented that successfully uses a hydride palladium catalyst system generated from [PdCl₂(PPh₃)₂] and HSi(OEt)₃. The Z to E isomerization was carried out smoothly and resulted in geometrically pure substituted olefins. Apart from the cis–trans isomerization of double bonds, the selective reduction of terminal olefins and activated alkenes was performed with excellent functional group tolerance in the presence of an amide-derived olefin ligand, and the products were obtained in high isolated yields (up to >99 %). Furthermore, the palladium/hydrosilane system was able to promote the reductive decarbonylation of benzoyl chloride when a (Z)-olefin with an aromatic amide moiety was used as a ligand.

An interesting example of a divergent catalysis with a copper(I) and amine-functional macromolecular polysiloxanes system was successfully presented in click chemistry. In this manuscript, we demonstrate the remarkable ability of the secondary amine-functional polysiloxane to induce oxidative coupling in the copper-mediated Huisgen reactions of azides and alkynes, thereby achieving good yields and selectivities. The click reactions mediated by a polysiloxane-supported secondary amine allow the preparation of novel heterocyclic compounds, that is, bistriazoles. Comparably, it is also surprising that the use of a diamine-functional polysiloxane as ligand led to a classic Huisgen [3+2] cycloaddition in excellent yields. From the results of the present amine-functional polysiloxanes-controlled Huisgen reaction or oxidative Huisgen coupling reaction to divergent products and the proposed mechanism, we suggested that the mononuclear bistriazole–copper complex stabilized and dispersed by the secondary amine-functional polysiloxane was beneficial to prevalent the way to oxidative coupling.

A novel metal-free intramolecular Brønsted-acid-catalyzed domino deprotection–hydrosilylation with hydrosilanes has been developed, and the unexpected Brønsted-acid-catalyzed intermolecular hydrolytic oxidation to functional siloxanes was described for the divergent and facile synthesis of functionalized siloxanes containing aldehyde motifs. We propose that these reactions proceed via neighboring acetal-assisted Si–H bond activation. In addition, a related reaction is expected to open up further opportunities for the development and application of functional organosilicon compounds by organocatalysis.

A detailed experimental investigation of an aza-Michael reaction of aniline and chalcone is presented. A series of Cinchona alkaloid-derived organocatalysts with different functional groups were prepared and used in the aza-Michael and retro-aza-Michael reaction. There was an interesting finding that a complete reversal of stereoselectivity when a benzoyl group was introduced to the cinchonine and cinchonidine. The chirality amplification vs. time proceeds in the quinine-derived organocatalyst containing silicon-based bulky group, QN-TBS, -catalyzed aza-Michael reaction under solvent-free conditions. In addition, we have demonstrated for the first time that racemization was occurred in suitable solvents under mild conditions due to retro-aza-Michael reaction of the Michael adduct of aniline with chalcone. These indicate the equilibrium of retro-aza-Michael reaction and aza-Michael reaction produce the happening of chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction under different conditions, which would be beneficial to the development of novel chiral catalysts for the aza-Michael reactions. Chirality, 2011. © 2011 Wiley-Liss, Inc.

A facile and practical methodology for the synthesis of synthetically useful diarylmethanol-based 1,4-diols and enantiomerically pure BINOL-derived diols with axial and sp³-central chirality has been developed through neighboring lithium-promoted [1,2]-Wittig rearrangement. The chirality transfer process shows a broad substrate scope in terms of the aromatic ether substituent, which allows access to a broad of range of chiral 1,1′-binaphthalene-2-α-arylmethanol-2′-ols with excellent enantioselectivities (>99 % enantiomeric excess) and yields (84–96 %). This should be considered as an available and attractive chiral source to design and prepare privileged ligands or catalysts.

Iron–palladium is a superior bimetallic catalyst in the presence of acetylacetone (Acac) with remarkable synergistic effect for the Michael-type Friedel–Crafts reactions of indoles with chalcones. This catalytic system has the advantages of mild reaction conditions, smaller amount of metal salts, high yields of the desired products and operational simplicity, which make it a useful and promising process for the synthesis of indole derivatives. Copyright © 2009 John Wiley & Sons, Ltd.

A novel chiral ionic liquid, compound 1, based on camphorsulfonic acid, was prepared. A catalytic amount of 1 readily promotes L-proline-catalyzed aldol reactions, with good chemoselectivity, both in H₂O and in organic solvents. Further, the aldol reaction of cyclohexanone with 4-nitrobenzaldehyde afforded 2-[hydroxy(4-nitrophenyl)methyl]cyclohexanone (6) in 98% yield with high enantioselectivity (94% ee) when large amounts of 1 (5 equiv.) were used as promoter.