Structural and magnetic properties of the phase transition in absorbed and non-absorbed copper(II) trans-1,4-cyclohexanedicarboxylate

A large amount of toluene can be absorbed into the 1-dimensional tunnels in copper(II) trans-1,4-cyclohexane dicarboxylate (Cu(trans-1,4-OOCC₆H₁₀C)) at room temperature, and it can be desorbed by evacuation at elevated temperatures. The reversible absorption/desorption behavior of toluene was studied by magnetic susceptibility measurements using SQUID magnetometer and by powder X-ray diffractometry with high-energy synchrotron radiation at SPring-8, Japan. The first order phase transition was observed at 160 K in the magnetic susceptibility curve for the empty (non-absorbed or desorbed) sample, and the structural difference between the low and high temperature phases was detected in the powder X-ray diffraction patterns. On the other hand, no phase transition was observed in fully toluene-absorbed sample, and the structure was similar to that of the low temperature phase of the empty sample. The absorption/desorption behavior observed in the present study coincides with the results of heat capacity measurements by adiabatic calorimetry reported previously.     

Conjugate addition of copper(I) aldimines to α,β-unsaturated carbonyl compounds — synthesis of 1,4-diketones

This paper describes the finding that BF₃ etherate effectuates the conjugate additions of copper(I) aldimines, generated in situ from lithium aldimines and Cu(I) halide, to α,β-unsaturated carbonyl compounds to produce 4-(N-alkylimino)-ketones, which give on acid hydrolysis 1,4-diketone derivatives.     

Studies on organic fluorine compounds. LIII. Preparation of functionalized trifluoromethylated compounds using 1-phenylsulfonyl-3,3,3-trifluoropropene

Reaction of 1-phenylsulfonul-3,3,3-trifluoropropene(1) with carbonyl-stabilized enolate anions smoothly proceeded to give the addition products(7) in good yield while with an alkyl-lithium or Grignard reagent the formation of the vinyl anion(8) was one of the reaction pathways. Reaction of 1 with the chiral nucleophiles(11, 16) was carried out to give the functionalized trifluoromethylated compounds(13, 7b) in 4-43% ee     

Efficient synthesis of optically active atropisomeric anilides through catalytic asymmetric N-arylation reaction

In the presence of (R)-DTBM-SEGPHOS-Pd(OAc)2 catalyst, N-arylation of ortho-tert-butyl-NH-anilides with 4-nitroiodobenzene proceeds with high enantioselectivity (89-95% ee) to give optically active atropisomeric anilides possessing N-C chiral axis. Furthermore, the intramolecular version of the present catalytic asymmetric N-arylation gave atropisomeric lactams with high optical purity (94-96% ee).     

Stereocontrolled synthesis of 7-hydroxy- and 7-acetoxy-PGI2: New stable PGI2 analogues

Stable analogues of PGI₂, 7-hydroxy- and 7-acetoxy-PGI₂, were synthesized from protected PGI₂ methyl ester $\text{1b}$via sulfoxides $\text{6a}$, $\text{6b}$ through stereocontrolled sulfoxide-sulfenate rearrangement.