Ir(III)‐Catalyzed C7‐Position‐Selective Oxidative CH Alkenylation of Indolines with Alkenes in Air

An efficient method for C7‐position‐selective alkenylation of N‐substituted indolines with alkenes is reported. Various 7‐alkenylindolines were obtained in moderate to excellent yields in air in the presence of catalytic amounts of [Cp*IrCl₂]₂, AgOTf, and Cu(OAc)₂. The protocol relies on the use of a carbonyl or carbamoyl group on the nitrogen atom of indoline as a directing group and is potentially applicable to the synthesis of 7‐alkenylindoles and 7‐alkylindoles.     

Facile Insertion of Carbon Dioxide into Cu2(μ‐H) Dinuclear Units Supported by Tetraphosphine Ligands

Reactions of meso‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm) with Cu^I species in the presence of NaBH₄ afforded di‐ and tetranuclear copper hydride complexes, [Cu₂(μ‐H)(μ‐dpmppm)₂]X ( 1 ) and [Cu₄(μ‐H)₂(μ₄‐H)(μ‐dpmppm)₂]X ( 2 ) (X=BF₄, PF₆). Complex 1 undergoes facile insertion of CO₂ (1 atm) at room temperature, leading to a formate‐bridged dicopper complex [Cu₂(μ‐HCOO)(dpmppm)₂]X ( 3 ). The experimental and DFT theoretical studies clearly demonstrate that CO₂ insertion into the Cu₂(μ‐H) unit occurred with the flexible dicopper platform. Complex 2 also undergoes CO₂ insertion to give a formate‐bridged complex, [Cu₄(μ‐HCOO)₃(dpmppm)₂]X, during which the square Cu₄ framework opened up to a linear tetranuclear chain.     

Oxidative Bond Cleavage of the Silicon–Silicon Bond of a Pentacoordinated Disilicate

The Si Si bond of a pentacoordinated disilicate was readily cleaved by treatment with 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone in the presence of sodium carbonate under mild conditions. The bond cleavage did not proceed under the same conditions after conversion of the disilicate into the corresponding monoanionic silylsilicate and neutral disilane by protonation. The difference in the charges of the Si Si bond compounds affects the reactivity toward an oxidant, resulting in the Si Si bond cleavage, considering that all of these compounds have a bond between pentacoordinated silicon atoms.     

Swelling–shrinking behavior of hydrated noncross‐linked copolymer films in response to photoreversible isomerizaton and metal complexation of spiropyran units of the copolymers

The copolymer of hydroxypropyl methacrylate (HPMA) and photochromic spiropyran methacrylate (SPMA) has been synthesized. The films of the copolymer (P(HPMA‐SPMA)) in a hydrated state showed reversible swelling–shrinking behavior in response to photoreversible isomerization and metal complexation of SPMA units in spite of covalently noncross‐linked copolymers. In addition, the protonated open form of the SPMA units of the copolymer was possibly stabilized thermodynamically by the HPMA units from ultraviolet–visible absorption measurement of the hydrated P(HPMA‐SPMA) film. On the other hand, the difference in color of the hydrated films between P(HPMA‐AABMA) and P(NIPMA‐AABMA), which was a copolymer of N‐isopropyl methacryl amide (NIPMA) and azobenzene methacrylate (AABMA) as a pH indicator, was suggestive of the interference of the proximal hydroxyl groups of the immobilized HPMA units with protonation of the AABMA units. The HPMA units of the copolymers also contributed to improvement of thermodynamic stability of the metal complexes with the SPMA units. Copyright © 2013 John Wiley & Sons, Ltd.     

Detection of oxygen addition peaks for terpendole E and related indole–diterpene alkaloids in a positive‐mode ESI‐MS

This report describes that a regular positive electrospray ionization mass spectrometry (MS) analysis of terpendoles often causes unexpected oxygen additions to form [M + H + O]⁺ and [M + H + 2O]⁺, which might be a troublesome in the characterization of new natural analogues. The intensities of [M + H + O]⁺ and [M + H + 2O]⁺ among terpendoles were unpredictable and fluctuated largely. Simple electrochemical oxidation in electrospray ionization was insufficient to explain the phenomenon. So we studied factors to form [M + H + O]⁺ and [M + H + 2O]⁺ using terpendole E and natural terpendoles together with some model indole alkaloids. Similar oxygen addition was observed for 1,2,3,4‐tetrahydrocyclopent[b]indole, which is corresponding to the substructure of terpendole E. In tandem MS experiments, a major fragment ion at m/z 130 from protonated terpendole E was assigned to the substructure containing indole. When the [M + H + O]⁺ was selected as a precursor ion, the ion shifted to m/z 146. The same 16 Da shift of fragments was also observed for 1,2,3,4‐tetrahydrocyclopent[b]indole, indicating that the oxygen addition of terpendole E took place at the indole portion. However, the oxygen addition was absent for some terpendoles, even whose structure resembles terpendole E. The breakdown curves characterized the tandem MS features of terpendoles. Preferential dissociation into m/z 130 suggested the protonation tendency at the indole site. Terpendoles that are preferentially protonated at indole tend to form oxygen addition peaks, suggesting that the protonation feature contributes to the oxygen additions in some degrees. © 2014 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons, Ltd.     

Rhodium(I)‐Catalyzed Cyclization of Allenynes with a Carbonyl Group through Unusual Insertion of a CO Bond into a Rhodacycle Intermediate

Rhodium(I)‐catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a C?O bond into the C(sp²)–rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, while β‐hydride elimination from the same intermediate gives products that contain fused five‐ and seven‐membered rings in high yields.     

Stable meso–meso‐Linked 2NH‐Corrole Radical Dimers as a Key Intermediate to Corrole Tape

While oxidation of 5,5′,15,15′‐tetramesityl‐10‐10′‐linked 3NH‐corrole dimer with DDQ gave the corresponding triply linked 2NH‐corrole tape, the use of an equimolar amount of p‐chloranil as a milder oxidant resulted in the formation of a 10‐10′‐linked neutral 2NH‐corrole radical dimer as a stable product. The stability of this peculiar product is ascribed largely to strong antiferromagnetic interaction of the two spins. Further oxidation of this diradical produced corrole tape, suggesting its involvement as a reaction intermediate to the corrole tape. Oxidation of 10‐10′‐linked bis‐pyridine‐coordinated Co^III corrole dimer with DDQ produced a cobalt corrole radical dimer and a doubly linked corrole dimer both as stable compounds bearing pyridine and cyanide axial ligands. This type of oxidative transformation involving neutral diradical intermediates is a unique reaction mechanism specific for corrole dimers.     

Polyether-bridged bis(tert-butyl nitroxide) paramagnetic hosts showing receptor ability to calcium(II) and barium(II) ions

The title compounds, Ph2bNO and Ph3bNO, were designed as a biradical paramagnetic host, and their chelation ability was confirmed by inclusion of a size-matched alkaline-earth metal ion. The crystal structures of [Ca(hfac)₂(Ph2bNO)] and [Ba(hfac)₂(Ph3bNO)] were determined, where Hhfac stands for 1,1,1,5,5,5-hexafluoropentane-2,4-dione. The solution electron paramagnetic resonance spectra showed switching behavior. Five lines were found for Ph3bNO and charecterized as the hyperfine splitting due to the two nitrogen atoms. After addition of barium(II) ion, the spectrum turned to be three lines. Removal of the barium ion recovered the five line pattern. The present system can be regarded as a reversible magnetic-coupling switch by means of a supramolecular technique.     

Chemical and genetic diversity of Ligularia virgaurea collected in northern Sichuan and adjacent areas of China. Isolation of 13 new compounds

Root chemicals and DNA sequences were analyzed for Ligularia virgaurea collected in the northern Sichuan Province and adjacent areas of China. Thirty-eight samples were found to contain five chemotypes, two known and three new ones. From samples of the new chemotypes, 13 new compounds were isolated, including 3 sesquiterpene dimers and some rearranged eremophilanes. The DNA sequences suggested that the chemotype differentiation had a genetic origin.