A first experimental approach to the 15O + α elastic scattering

The ¹⁵O(α,α)¹⁵O elastic scattering is investigated using a ¹⁵O radioactive beam and a He gas cell limited by Mylar windows. The width of a ¹⁹Ne state at an excitation energy of 5.35MeV is measured as Γ_α = 3.2±1.6keV, in agreement with charge symmetry estimate.     

Rhodium(I)‐Catalyzed Sequential C(sp)?C(sp3) and C(sp3)?C(sp3) Bond Formation through Migratory Carbene Insertion

A Rh^I‐catalyzed three‐component reaction of tert‐propargyl alcohol, diazoester, and alkyl halide has been developed. This reaction can be considered as a carbene‐involving sequential alkyl and alkynyl coupling, in which C(sp) C(sp³) and C(sp³) C(sp³) bonds are built successively on the carbenic carbon atom. The Rh^I‐carbene migratory insertion of an alkynyl moiety and subsequent alkylation are proposed to account for the two separate C C bond formations. This reaction provides an efficient and tunable method for the construction of all‐carbon quaternary center.     

A New and Facile Synthesis of Novel Pyrazolothienopyrimidines and Imidazopyrazolothienopyrimidines

4‐Amino‐3‐methyl‐1‐phenyl‐1H‐thieno[2,3‐c]pyrazole‐5‐carboxamide ( 5 ), which was synthesized by an innovative method, was used as a versatile precursor for synthesizing pyrazolothienopyrimidines and imidazopyrazolothienopyrimidines compounds. Reaction of amino thienopyrazole carboxamide 5 with triethyl orthoformate afforded thienopyrazolopyrimidine 6 . Chlorination of the latter compound, using phosphorus oxychloride afforded the chloro pyrazolothienopyrimidine 7 , which underwent nucleophilic substitution reactions with various primary and secondary amines to give the alkyl (aryl) amino pyrimidine compounds 8a–d . On the other hand, the reaction of chloropyrimidine 7 with thiourea afforded the pyrimidine thione compound 9 , which was alkylated with α‐halogentaed compounds to afford the S‐alkylated derivatives 10a–c . Also, chloroacetylation of the amino carboxamide 5 using chloroacetyl chloride yielded the chloromethyl pyrazolothienopyrimidine 12 , which underwent nucleophilic substitu‐ tion reactions with various primary and secondary amines to afford the alkyl (aryl) aminomethyl compounds 13a–f . The latter Compounds underwent Mannich reaction to give imidazopyrimidothieno‐ pyrazoles 14a–c . The newly synthesized compounds and their derivatives were fully characterized by elemental and spectral analysis.     

Ruthenium‐Catalyzed Metathesis Cascade Reactions in Natural Products Synthesis

In this account, we provide a brief summary of recent developments in ruthenium‐catalyzed metathesis cascade reactions towards the total synthesis of natural products. We also highlight recent progress from our own laboratory regarding the synthesis of securinega alkaloids and humulanolides, which has resulted in the development of novel ruthenium‐catalyzed metathesis cascade reactions. Inspired and guided by the pioneering and elegant research conducted in this area, we developed a regio‐controlled relay dienyne metathesis cascade reaction and a cyclobutene‐promoted RCM/ROM/RCM cascade reaction for the synthesis of securinega alkaloids and humulanolides, respectively.     

Rhodium(II) carbene-mediated modification of 2-deoxystreptamine surrogates

Rhodium(II)-catalyzed decomposition of carbene precursors grafted to the alcohol of diaminocyclopentanols promotes clean formation of a C-N bond via 1,6-insertion into an adjacent carbamate or azide. These modifications of 2-deoxystreptamine surrogates might give rise to aminoglycoside mimics where the two nitrogen atoms will be differentiated.     

Arylation of styrene derivatives using aryliron complexes [CpFe(CO)2Ar] revealed by density functional theory calculations: Fe(II)-assisted group exchange through Fe-C bond cleavage and Fe-X bond formation

The detailed mechanism for arylation of styrene or its α-CF₃ substituted analog using aryliron complex [CpFe(CO)₂Ar] was studied using density functional theory calculations. Results of calculations show that the arylation mechanism mainly involves three steps: (1) a ligand exchange process between a CO and styrene or its derivative; (2) migration of Ar group from Fe to β-C of styrene; (3) β-H (or β-F) elimination and dissociation of the stilbene derivative from the CpFeHCO (or CpFeFCO) moiety. Both of Steps (2) and (3) experience a similar four-memberred cyclic transition state. The d_π-p_π interaction stabilizes the CC π coordinated complexes and the agostic interaction plays an important role in stabilizing intermediates and promoting elimination of the β-H (or β-F if available). For arylation of the α-CF3 substituted styrene, our calculations clarified that the dissociation of ethylene derivatives to give PF (product for β-F elimination) is kinetically and thermodynamically more favorable than to give PH (product for β-H elimination), which is the determined step for the selectivity of the final products.     

Synthesis and structure of new compounds with Pt-Ga bonds: Insertion of the bulky gallium (I) bisimidinate Ga(DDP) into Pt-Cl bond

Reactions of the sterically bulky mono-valent group 13 bisimidinate gallium(I), Ga(DDP) (1) (DDP = 2-{(2, 6-diisopropylphenyl)amino}-4-{(2, 6-diisopropylphenyl)imino}-2-pentene, HC(CMeNC₆H₃-2,6-ⁱPr₂)₂) with olefin supported group 10 complexes, [(diene)PtCl₂] [diene = 1,5-cyclooctadiene (COD), endo-dicyclopentadiene (dcy)] and [(COD)Pd(Me)(OTf)] (OTf = O₃SCF₃) are reported. These reactions afforded [(COD)Pt(Cl){ClGa(DDP)}] (2), [(dcy)Pt(Cl){ClGa(DDP)}] (3) and [(DDP)Ga(Me)(OTf)] (4) in moderate yields. Compounds 2-4 were characterized by elemental analysis, NMR (¹H, ¹³C) spectroscopy and also by single crystal X-ray structural analysis. The solid state structures of complexes 2 and 3 reveal the oxidative insertion of Ga(DDP) into the Pt-Cl bond without altering the π-coordinated double bonds in the olefin.     

Inelastic scattering on 12Be and disappearance of the N = 8 magic number

Experimental studies on in-beam γ-ray spectroscopy using a ¹²Be radioactive beam are presented. Inelastic scattering of the neutron-rich ¹²Be nucleus on ²⁰⁸Pb, ¹²C, and (CH₂)_n targets has been studied by measuring de-excitation γ-rays in coincidence with scattered particles. The level schemes and transition probabilities are determined for low-lying excited states in ¹²Be. The present paper presents a brief review of the spectroscopic results, which may be associated with the N = 8 shell quenching near the drip line. Received: 1 May 2001 / Accepted: 4 December 2001     

Spins and lifetimes of levels in 55Mn

The study of excited ⁵⁵Mn levels with the ⁵²Cr(α, pγ) reaction was extended to levels up to 3161 keV. With a Ge(Li) detector, DSA measurements in gold-backed targets were made, as well as angular correlations; both of these experiments were done in coincidence with protons detected near 180°. A multiple-detector NaI(Tl) array was also used in the same reaction geometry for better γ-ray detection efficiency. Mean lifetimes of 12 levels from 2727 to 3161 keV are reported. Spins and sometimes parities of the following levels were deduced from the angular-correlation analyses and lifetime results: 1885 keV, $\text{7}\text{2}$^?; 2199 keV, $\text{7}\text{2}$(^?); 2311 keV, ($\text{13}\text{2}$); 2366keV, $\text{5}\text{2}$^?; 2727 keV, $\text{7}\text{2}$; 2823 keV, $\text{9}\text{2}$. Multipole mixing ratios and M1 and E2 transition rates of the radiations from these and from the 1292 keV level are presented. The similarity of the low-lying level structure and of interlevel transitions in ⁵⁵Mn to those in certain other f_{$\text{7}\text{2}$}³ nuclei is examined.     

Dispersion relations and low-energy elastic scattering of charged particles from nuclei: (II). Application to N-4He scattering

A “Coulomb-modified” dispersion relation is applied to low-energy p-⁴He forward elastic scattering. To check the validity of the modification, the results are compared with those deduced from n-⁴He elastic scattering. Completely analogous information is obtained for the two processes. The exchange of three bound nucleons is found to contribute strongly to N-⁴He forward scattering. The corresponding ⁴He-³H-p and ⁴He-³He-n coupling constants are evaluated as R_p = 3.8±0.3 and R_n = 3.0±0.3, respectively. These constants are related to the strength of the asymptotic wave function of nucleons in ⁴He and thus to the tail of the nucleon distribution. A comparison of R_p with the empirical proton distribution in ⁴He as deduced from e-⁴He elastic scattering shows excellent agreement. From R_p and R_n the effective ranges of the singlet ³H-p and ³He-n interactions in the ground state of ⁴He are determined to be equal, in accordance with charge symmetry, and to have a value of r_eff = 1.072±0.006 fm.