Iridium-Catalyzed Reductive (3+2) Annulation of Lactams Enabling the Rapid Total Synthesis of (±)-Eburnamonine

A reductive (3+2) annulation of lactams through iridium-catalyzed hydrosilylation and photoredox coupling with α-bromoacetic acid was developed. The iridium-catalyzed hydrosilylation of the lactam carbonyl group and subsequent elimination provide a transient cyclic enamine, which undergoes iridium-catalyzed photoredox coupling with α-bromoacetic acid in a one-pot process. The developed conditions show high functional-group tolerance and provide cyclic N,O-acetals containing a quaternary carbon center. The resulting N,O-acetals undergo a variety of acid-mediated nucleophilic addition reactions via iminium ions to give substituted cyclic amines. The developed sequence including reductive (3+2) annulation and acid-mediated nucleophilic addition was successfully applied to the four-step total synthesis of (±)-eburnamonine.     

An Efficient Synthesis of 3‐(1H‐Tetrazol‐5‐yl)coumarins (=3‐(1H‐Tetrazol‐5‐yl)‐2H‐1‐benzopyran‐2‐ones) via Domino Knoevenagel Condensation,Pinner Reaction,and 1,3‐Dipolar Cycloaddition in Water

A novel straightforward synthesis of 3‐(1H‐tetrazol‐5‐yl)coumarins (=3‐(1H‐tetrazol‐5‐yl)‐2H‐1‐benzopyran‐2‐ones) 6 via domino Knoevenagel condensation, Pinner reaction, and 1,3‐dipolar cycloaddition of substituted salicylaldehydes (=2‐hydroxybenzaldehydes), malononitrile (propanedinitrile), and sodium azide in H₂O is reported (Scheme 1 and Table 2). This general protocol provides a wide variety of 3‐(1H‐tetrazol‐5‐yl)coumarins in good yields under mild reaction conditions.     

Domino allylation and cyclization of ortho-alkynylbenzaldehydes with allyltrimethylsilane catalyzed by Pd(II)-Cu(II) bimetallic systems

The reaction of ortho-alkynylated benzaldehydes 1 with allyltrimethylsilane under the Pd(OAc)₂-CuCl₂ catalyst system gave the isochromene derivatives 2 together with the chlorinated products 3. When the reaction was conducted in the presence of half equiv of H₂O, the formation of 3 was suppressed and 2 was obtained in good to high yields. When the reaction of 1a was carried out with trimethylsilylcyanide instead of allylsilane, the cyano group-substituted isochromene 9 was obtained in 94% yield.     

Laccase initiated oxidative domino reactions for the efficient synthesis of 3,4-dihydro-7,8-dihydroxy-2H-dibenzofuran-1-ones

Laccase initiated domino reactions of cyclohexane-1,3-diones with catechols using air as an oxidant afford 3,4-dihydro-7,8-dihydroxy-2H-dibenzofuran-1-ones with yields ranging from 70% to 97%.     

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     

The versatile role of norbornene in C-H functionalization processes: concise synthesis of tetracyclic fused pyrroles via a threefold domino reaction

The synthesis of novel tetracyclic fused pyrroles from 1-(2-iodophenyl)-1H-pyrrole and various bromoalkyl-aryl alkynes via a palladium(0)-catalyzed and norbornene-mediated threefold domino reaction is reported. PdCl₂ and tri-2-furylphosphine (TFP) in the presence of norbornene and Cs₂CO₃ in CH₃CN at 90 °C gave a variety of tetracyclic fused pyrroles in usually high yields. In the described reaction sequence two of the three carbon-carbon bonds are formed by functionalization of an unactivated aryl C-H bond.     

Synthesis of novel annulated uracils via domino Knoevenagel-hetero-Diels-Alder reaction in aqueous media

An efficient synthesis of tetracyclic uracil derivatives (polycyclic pyrans) is achieved via domino Knoevenagel-hetero-Diels-Alder reactions of O-propargylated salicylaldehyde derivatives with 1,3-dimethylbarbituric acid in water as solvent in the presence of CuI. The products are formed in good yields.     

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.     

High-spin states in the isotones 89Zr, 91Mo and 93Ru populated in α-particle-induced reactions

The reactions (α, 3nγ) and (α, α′nγ) on ⁸⁸Sr, ⁹⁰Zr and ⁹²Mo were used to populate excited states in ⁸⁹Zr, ⁹¹Mo and ⁹³Ru. The de-excitation of these states was studied by in-beam γ-ray spectroscopy. The short-lived radioactivity of the ⁹²Mo target was measured in order to study the decay of ⁹³Ru. Many new levels were observed, particularly in ⁹¹Mo. They are interpreted as due to the coupling of a $\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ neutron hole with known excited states in ⁹⁰Zr, ⁹²Mo and ⁹⁴Ru.