A spiroketal bisphosphine (SKP) derived chiral digold complex is identified as a powerful catalyst for the highly diastereo- and enantioselective synthesis of spirocyclopropyloxindoles from diazooxindoles and a broad range of alkenes, including both cis and trans 1,2-disubstituted alkenes.

A simple, new type of chiral sulfinamide monophosphines, the so-called Ming-Phos ligands, is reported; these ligands could be easily prepared from inexpensive and commercially available starting materials. The Ming-Phos ligands performed well in the enantioselective gold-catalyzed cycloaddition reaction of 2-(1-alkynyl)-alk-2-en-1-ones with nitrones. Both enantiomers of the products could be obtained in good yields and with excellent diastereo- and enantioselectivity through transformations that were catalyzed by gold complexes derived from two diastereomers of Ming-Phos ligand M5 (Ar=1-naphthyl).

A highly enantioselective Strecker reaction of difluoromethyl and trifluoromethyl ketoimines was developed. Remarkable fluorine effect on the reactivity and selectivity is observed and discussed.

The novel framework [{Co(en) 2 } 2 Sb III 8 V IV 14 O 42 (H 2 O)]•6H 2 O is composed of two-dimensional arrays of {Sb III 8 V IV 14 O 42 (H 2 O)} clusters interlinked via {Co(en) 2 } bridging groups; such antimony-vanadium clusters with antimony and vanadium in low oxidation states were previously unknown.Keggin-type heteropolycomponds find application as heterogeneous catalysts in a variety of oxidation reactions. 1 However, the biggest drawback of heteropolycompounds, which limits their application as heterogeneous catalysts, is the structural decomposition, which occurs in air at temperatures close to 300 ЊC. 2 It is interesting that heteropolycompounds containing antimony oxide often play an important role in heterogeneous oxidation catalysis and antimony cations have a stabilizing effect on polyoxometalates at high (>450 ЊC) temperatures. 3 The reports of antimony-containing polyoxometalates are rather scarce. However, some polyoxometalates of antimonycontaining polyoxotungstates 4-9 and antimony-containing polyoxomolybdates 10 have been reported. Here we report the synthesis and X-ray crystal structure analysis of the first antimony-containing polyoxovanadium compound { [{Co-(en) 2 } 2 Sb III 8 V IV 14 O 42 (H 2 O)]ؒ6H 2 O} (1). Compound 1 was synthesized hydrothermally as black rhombus crystals in 46% yield (based on Sb). A mixture of Sb 2 and H 2 O (20 mL) in a molar ratio of 1 : 2 : 2 : 2 : 1292 was stirred for 120 min and then adjusted to pH = 9.0 using en. It was sealed in a 30 mL Teflon-lined reactor and kept at 160 ЊC for nine days. H 2 C 2 O 4 ؒ2H 2 O was used as a reducing agent and it was necessary to maintain the pH of the reaction. After being cooled to room temperature, black rhombus crystals were isolated. The elemental analysis, ICP and IR spectra † in combination with the X-ray single-crystal analysis ‡ confirmed the formula of 1, [{Co(enThe 2D extended structure (Fig. 1) of 1 consists of [Sb III 8 -V IV 14 O 42 (H 2 O)] 4Ϫ sphere-like clusters, each one of which is linked to four other neighbouring [Sb III 8 V IV 14 O 42 (H 2 O)] 4Ϫ units by four [Co(en) 2 ] 2ϩ bridges, generating a two-dimensional network of [-{Sb III 8 V IV 14 O 42 (H 2 O)}-µ-{Co(en) 2 }-{Sb III 8 V IV 14 O 42 -(H 2 O)}-] ∞ arrays. The octahedral geometry around each cobalt is completed by four nitrogen donors from two en molecules [Co-N = 2.125(7)-2.147(7) Å] and two trans-µ-oxo groups (O3, O20) [Co-O = 2.106(5), 2.121(5) Å]. The H 2 O molecules occupy the parallelogrammic cavities. The spherical structure (Fig. 2) of each [Sb III 8 V IV 14 O 42 -(H 2 O)] 4Ϫ cluster consists of 14 condensed vanadium oxygen square pyramids (VO 5 ) and 8 trigonal pyramids (SbO 3 ), and includes at its center a statistically disordered H 2 O molecule.