N-Substituted 2-aza-[3]-ferrocenophanes were easily synthesized from 1,1′-ferrocenedicarbaldehyde and aliphatic amines in high yields. One of the ferrocenophanes served as a ligand for the copper-catalyzed oxidative coupling of 2-naphthol derivatives to give the products in good yields with up to 92 % ee, and it also efficiently catalyzed the asymmetric Michael addition reaction as an organocatalyst.

The palladacycle-catalyzed esterification of a variety of aldehydes with alcohols was developed. This reaction allows formation of esters in moderate to excellent yields not only for various aldehydes but also alcohols. In addition, the esterification could proceed well under mild conditions with a low catalyst loading of 0.0625 mol%. Copyright © 2013 John Wiley & Sons, Ltd.

An efficient and generally applicable protocol for the palladacycle-catalysed arylation or K₂CO₃-promoted arylmethylation of diisopropyl H-phosphonate has been developed. The remarkable features of the palladacycle-catalysed arylation reaction include wide substrate scope (aryl iodides, bromides and chlorides), significant shortening of the reaction time (2 or 3 h) and a low catalyst loading of 1 mol-%. Note that with the base K₂CO₃ as promoter, arylmethylation could be achieved without any palladium catalyst. Moreover, the first example of a palladium-catalysed phosphonation of inactive electron-rich aryl chlorides with tBuOK as the base has been realized. This result could be considered an important improvement and complement to earlier work of Montchamp and Han, whose catalytic systems are typically compatible with electron-deficient and electron-neutral aryl chlorides.

A novel selective fluorescence probe that contains 2-p-phenylimidazo[4,5-f][1,10]phenanthroline and a viologen unit linked by a flexible chain was synthesized and found to be able to select zinc ions with a clear fluorescence enhancement and a large stokes shift in aqueous solution. This probe can also be designed as an on–off–on molecular switch by the formation and rupture of a supramolecular nanocapsule with cucurbit[8]uril (CB[8]) in aqueous solution.

The first palladium-catalyzed protocol for the denitrated coupling reaction of nitroarenes with phenols has been developed, achieving unsymmetrical diaryl ethers in moderate to excellent yields. The cyclopalladated ferrocenylimine (catalyst Ic) exhibited highly catalytic activity for this transformation with low catalyst loading (0.75 mol%) and short reaction time (2 h). The efficiency of this reaction was demonstrated by its compatibility with a range of groups. Moreover, the rigorous exclusion of air or moisture was not required in these transformations. Copyright © 2013 John Wiley & Sons, Ltd.

An efficient, simple way to synthesize aminopyridine derivatives is presented, based on Buchwald–Hartwig aminations. Using 1 mol% N-heterocyclic carbene adduct of cyclopalladated ferrocenylimine in the presence of 1.5 equiv. ^tBuOK as base in dioxane at 110°C offered moderate to excellent yields in the reaction of chloropyridines with primary and secondary amines, including sterically hindered amines and alkyl amines.

An efficient palladacycle-catalyzed aromatic carbonylation reaction of aryl formates with aryl iodides or bromides has been developed. Commercially available and easily prepared aryl formates were employed as carbonyl sources without the use of external carbon monoxide. The present catalytic system shows broad functional group tolerance and affords aryl benzoate derivatives in good to excellent yields.

Due to using (R)- or (S)-α-methylbenzylamine as a chiral auxiliary, and low-temperature regime for reduction of the intermediate ferrocenyl-mono- or 1,1′-bis-ketimines, the corresponding secondary mono- or 1,1′-bis-amines were prepared with high diastereoselectivity. Removal of the α-methylbenzyl group afforded the optically active primary mono- and bis-ferrocenylethylamines in high yields. The absolute configuration of (R,R)-3a and (S,S)-3b was determined by X-ray single crystal diffraction.

The tricyclohexylphosphane adduct of cyclopalladated ferrocenylimine I exhibited high catalytic activity in the one-pot borylation/Suzuki–Miyaura coupling (BSC) reaction with low catalyst loading (2 mol-%). Various biaryls were obtained in good to excellent yields for 37 examples. This process was applied to aryl and heteroaryl halides (Br and Cl) containing a variety of functional groups and did not require an excess amount of phosphane ligand and the addition of the palladium catalyst in the second step.

The cyclopalladated ferrocenylimine adducts Ia, Ib, Ic were evaluated in the Suzuki cross-coupling reaction of benzyl halides with arylboronic acids. The tricyclohexylphosphine adduct Ia exhibited highly catalytic activity for the coupling of aryl and heteroaryl boronic acids containing various functional groups with benzylic bromides and chlorides (up to 99% yield), furnishing diarylmethane derivatives with low catalyst loading (1 mol%). It is worth noting that catalyst Ia can be reused eight times without losing its catalytic activity. Copyright © 2012 John Wiley & Sons, Ltd.

An efficient and facile protocol for palladacycle-catalyzed chlorination of 2-arylbenzoxazoles was developed. The results represent the first examples involving the palladacycle as the catalyst for such chlorination. This chlorination was not a ligand-directed ortho-CH activation, but an electrophilic substitution process at the para-position of the nitrogen atom in the benzo ring of benzoxazole moiety, the regiochemistry of which had been confirmed by HMBC spectral analysis. The catalytic system could tolerate various halogen atoms, such as F, Cl and Br, affording the corresponding products in moderate to excellent yields.

An efficient and facile protocol for the annulation of o-halobenzaldehyde derivatives with diverse internal alkynes has been developed using cyclopalladated ferrocenylimine as the catalyst, and the indenones as the products could be obtained in moderate to good yields. It was found for the first time that the addition of benzoic acid could remarkably speed up the reaction process. Copyright © 2011 John Wiley & Sons, Ltd.

A series of carbene adducts of cyclopalladated ferrocenylimine were prepared and evaluated in the cross-coupling reaction of aryl halides with Grignard reagents (the Kumada reaction). Complex d exhibited high catalytic activity for the coupling of aryl chlorides with sterically hindered Grignard reagents and the reaction tolerated various functional groups. A wide range of biaryls were efficiently obtained in good to excellent yields in the presence of 0.5 mol-% catalyst under mild reaction conditions.

Two water-soluble palladium (II) complexes 2 and 4 have been synthesized from easily available 2-arylnaphthoxazole derivatives. They were successfully applied to the Suzuki coupling of aryl bromides with phenylboronic acid in water at 100 °C under phosphine-free conditions. Copyright © 2008 John Wiley & Sons, Ltd.