Haiying Zhao

Synthesis, complexation of 1,2,3-(NH)-triazolylferrocene derivatives and their catalytic effect on thermal decomposition of ammonium perchlorate

Ferrocenyl 1,2,3-triazoles 3a–3f and their Cu(II) or Zn(II) complexes have been synthesized and characterized. Compound 3d was structurally determined by X-ray crystallography. The DTA and TG measurements confirm the obvious catalytic effect of the representative compounds 3a and 3b on the decreasing of the decomposition temperature of ammonium perchlorate (AP) (by 32.3 and 36.2 °C respectively), whereas the Cu or Zn complexes of 3a lowers the thermal decomposition temperature of AP more dramatically, by 60.6 and 61.9 °C respectively. So ferrocenyl 1,2,3-triazoles 3a–3f and their Cu(II) or Zn(II) complexes are a kind of potentially high-burning-rate catalyst.

CuBr-promoted formal hydroacylation of 1-alkynes with glyoxal derivatives: an unexpected synthesis of 1,2-dicarbonyl-3-enes.

An efficient and concise protocol has been developed for the highly regio- and stereoselective synthesis of E-1,2-dicarbonyl-3-ene derivatives by a copper-promoted reaction of 1-alkynes with α-carbonyl aldehydes in the presence of morpholine. The products obtained are believed as the formal hydroacylation of the triple bond.

Synthesis of allene ferrocenes through CuI-mediated Crabbé homologation reaction

A concise and efficient method for the synthesis of bifunctional allene ferrocenes based on the modified Crabbe homologation reaction of ferrocenylacetylenes with paraformaldehyde promoted by CuI was developed. The presented synthesis proceeded readily with high compatibility of sensitive functional groups on the cyclopentadiene ring providing good to excellent yields of the desired products.

tert-BuOK-Catalyzed condensation of ethyl diazoacetate to aldehydes and palladium-catalyzed 1,2-hydrogen migration for the synthesis of β-ketoesters under solvent-free conditions

A mild and convenient method for the condensation of ethyl diazoacetate (EDA) with aldehydes catalyzed by tert-BuOK under solvent-free conditions was developed. The corresponding α-diazo-β-hydroxy esters were further converted into β-ketoesters through palladium-catalyzed 1,2-hydrogen migration under neat conditions. The two-step transformation exemplifies a simple method for the efficient and green synthesis of β-ketoesters.

Iodine-mediated highly regio- and stereoselective iodoamination of ferrocenyl allene: an approach for the synthesis of ferrocene-containing allylic amines.

A straightforward and efficient protocol for the highly regio- and stereoselective synthesis of ferrocene-containing allylic amine derivatives via an iodine-mediated iodoamination of ferrocenyl allene was developed. The regio- and stereoselectivity of this reaction may be controlled by the steric effect of the bulky ferrocene group.

Synthesis, Electrochemical, and Thermal Properties of [3]Ferrocenophane-Containing Chalcone Derivatives

[3]Ferrocenophane-containing chalcone derivatives with benzene ring (3a–3d) or naphthalene ring (3e–3f) were synthesized and characterized. The potentials for [3]ferrocenophane-containing chalcones cathodically shifted ~70–80 mV compared with those of ferrocene-containing chalcones, indicating easier oxidation by loss of an electron for the former. The thermal behaviours of the prepared compounds were studied by differential scanning calorimetry and polarizing optical microscopy. Compound 3f with terminal alkyl chain of 14 carbon atoms displayed mesophases, whereas other compounds were non-mesomorphic and showed either crystal polymorphic phase transitions or simple melting and freezing process in the heating and cooling cycles.

Palladium-catalyzed three-component reaction of ferrocenyl allenes, aryl iodides and active methylene compounds: regio- and stereoselective synthesis of (E)-alkenylferrocenes

A concise protocol for the synthesis of (E)-alkenylferrocene derivatives based on the palladium-catalyzed three-component reaction of ferrocenyl allenes, aryl iodides and active methylene compounds was developed. This transformation exemplifies a simple method for the efficient synthesis of various mono- or bisallyl-substituted alkenylferrocenes in good yields with excellent regio- and stereoselectivities.

Efficient solvent-free synthesis of tertiary propargylic alcohols from arylacetylenes and ketones promoted by tert-BuOK

A mild and efficient method for the alkynylation of arylacetylenes with ketones promoted by tert-BuOK under solvent-free conditions was developed. The present green synthesis was applicable to many kinds of aromatic and aliphatic ketones providing good to excellent yields of tertiary propargylic alcohols.Graphical abstractA mild and efficient method for the alkynylation of arylacetylenes with ketones promoted by tert-BuOK under solvent-free conditions was developed. The present green synthesis was applicable to many kinds of aromatic and aliphatic ketones providing good to excellent yields of tertiary propargylic alcohols.

Rh2(OAc)4-catalyzed 2,3-migration of β-ferrocenecarboxyl α-diazocarbonyl compounds: an efficient synthesis of ferrocene-containing α,β-unsaturated esters

A series of β-ferrocenecarboxyl α-diazocarbonyl compounds were prepared by the reaction of ferrocenoyl chloride with β-hydroxyl α-diazocarbonyl compounds in the presence of pyridine. The diazo decomposition of these ferrocene-containing diazocarbonyl compounds with Rh2(OAc)4 resulted in 2,3-ferrocenecarboxyl migration to give ferrocene-containing α,β-unsaturated esters in high yields.

Regio- and stereoselective synthesis of ferrocene-containing β-iodoallylic esters and ethers from the iodofunctionalization of ferrocenylallene with carboxylic acids, phenols, and alcohols.

The iodofunctionalization of ferrocenylallene with carboxylic acids, phenols, and alcohols is described. The reaction proceeds smoothly in the presence of molecule iodine as a halonium promoter and using various carboxylic acids, phenols, and alcohols as nucleophiles to give the corresponding ferrocene-containing β-iodoallylic ester and ether products in moderate to high yields and with high regio- and stereoselectivities. It can be envisaged that the regio- and stereoselectivity of this reaction may be controlled by the steric effect of the bulky ferrocene group. The presence of the C-I bond in the corresponding products makes these molecules highly attractive from a synthetic point of view, as it provides an opportunity for further transformations. Thus, palladium-catalyzed Heck coupling, Suzuki coupling, Sonogashira coupling, and copper-catalyzed click reactions were carried out successfully.