Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Rhodium-catalyzed addition of arylstannanes to carbon-heteroatom double bond

The addition of arylstannanes to the carbon-heteroatom double bond in the presence of a catalytic amount of a cationic rhodium complex ([Rh(cod)(MeCN)₂]BF₄) was examined. The reactions of aldehydes, α-dicarbonyl compounds, and N-substituted aldimines with the arylstannanes gave corresponding alcohols, α-hydroxy carbonyl compounds, and amines, respectively. An arylrhodium complex generated by the transmetalation with the arylstannane was probably the active catalytic species.     

Gamma-ray spectroscopy of the neutron-rich Ni region through heavy-ion deep-inelastic collisions

Nuclei in the neutron-rich Ni region have been studied by γ-ray spectroscopy. Gamma-rays emitted from isomers, with T _1/2 > 1 ns, produced in heavy-ion deep-inelastic collisions were measured with an isomer-scope. The nuclear structure of the doubly magic ⁶⁸Ni and its neighbor ^69,71Cu is discussed on the basis of the shell model. Future experiments for more neutron-rich Ni nuclei are also viewed. Received: 1 May 2001 / Accepted: 4 December 2001     

Outflow refreshment angiography: A bright blood, bright static tissue technique

A new “bright blood” strategy, outflow refreshment imaging, is introduced in which a number of overlapping slices are excited in rapid succession. Flowing spins that refresh each overlapped slice portion contribute a bright signal. Additionally, static tissue in each non-overlapped slice portion also yields a bright signal. However, the flow/static contrast is comparable to that produced in inflow refreshment images, and angiograms can be generated by conventional maximum intensity projection processing. The dual ability to visualize angiograms and static tissue images is a major benefit of the strategy. Computer simulations of flow sensitivities and in vivo results are presented which compare the outflow and inflow refreshment imaging strategies.     

Novel dinucleoside phosphotriester unit conjugated with an intercalative moiety in a stereospecific manner enhances thermal stability of an alternate-stranded triple helix

A novel phosphoramidite synthon of a dinucleoside phosphotriester unit bearing an intercalative moiety at its internucleotide linkage in a stereospecific manner was prepared and successfully incorporated into the middle portion of α-β chimeric oligoDNA. One of the resulting stereoisomeric chimera DNAs strongly enhances the thermal stability of an alternate-stranded triplex formed between the chimera and a double-stranded DNA.     

Anisotropic giant magnetoresistance originating from the π-d interaction in a molecule

We synthesized TPP[Fe^III(Pc)(CN)₂]₂, PTMA_x[Fe^III(Pc)(CN)₂]·y(MeCN), and PXX [Fe^III(Pc)(CN)₂], a new series of charge-transfer salts containing the axially-substituted phthalocyanine (Pc), [Fe^III(Pc)(CN)₂]⁻. In this molecular unit, the π conduction electron derived from the Pc-ring coexists with the d electron which is a potential source of a local magnetic moment. Therefore various phenomena associated with the interplay between local magnetic moments and conduction electrons are expected. We observed the giant negative magnetoresistance (GNMR) in all the three salts. The GNMR is highly anisotropic for the magnetic-field direction, and reflects the g-tensor anisotropy of the local magnetic moment in the [Fe^III(Pc)(CN)₂]⁻ unit. This indicates that the GNMR in these salts originates from the strong π-d interaction in the [Fe^III(Pc)(CN)₂]⁻ unit.     

Rhodium-catalyzed carbonylation of 2-alkynylbenzylamine: a new route to the synthesis of benzazepinones

Rhodium-catalyzed carbonylation of 2-alkynylbenzylamines under water-gas shift reaction conditions gives a seven-membered heterocyclic product, 2,4-disubstituted-1,4-dihydrobenz[c]azepin-3-ones, in a good yield.     

Carbonyl allylations by 3-halopropenes or 2-propenyl mesylate with tin(IV) chloride and tetrabutylammonium iodide

2-Propenyl tin species, prepared from 3-halopropenes or 2-propenyl mesylate with tin(IV) chloride and tetrabutylammonium iodide in dichloromethane, causes nucleophilic addition to aldehydes to produce the corresponding homoallylic alcohols.