Asymmetric synthesis of highly functionalized γ-lactams through an organocatalytic aza-Michael–Michael reaction cascade using fumaric acid amide esters as multi-reactive substrates

We developed a novel method for the asymmetric synthesis of highly functionalized γ-lactams through an organocatalytic aza-Michael–Michael reaction cascade using fumaric acid amide esters as multi-reactive substrates. Using chiral primary or secondary amine organocatalysts, we obtained two types of γ-lactams with three contiguous chiral centers in moderate to good yield with excellent enantioselectivity and diastereoselectivity.     

Essential Structure of Opioid κ Receptor Agonist Nalfurafine for Binding to κ Receptor 1: Synthesis of Decahydroisoquinoline Derivatives and Their Pharmacologies

On the basis of the three-dimensional pharmacophore model of opioid κ agonists, we simplified the structure of nalfurafine (selective κ agonist) to find the essential structural moieties for binding the opioid receptors, especially κ receptor type. As a result, we found that the trans-fused decahydroisoquinoline derivatives without a phenol ring bound the opioid receptor in micromolar order and that both the amide side chain and the nitrogen substituted by the cyclopropylmethyl group were indispensable moieties for eliciting the κ selectivity. The simple decahydroisoquinoline without amide side chain also bound the opioid receptor without receptor type selectivity, suggesting that the message-address concept would be applicable to even these simple derivatives. These findings that the simple decahydroisoquinoline derivatives showed the affinities for the opioid receptors, especially some of the compounds showed κ selectivity, are the first example in the opioid field.     

Synthesis and complexing properties of double armed diaza‐15‐crown‐5 and diaza‐18‐crown‐6 ethers having 4′‐hydroxy‐3′,5′‐disubstituted benzyl groups

A series of double armed diaza‐15‐crown‐5 ethers (9a ‐ 16a) and diaza‐18‐crown‐6 ethers (9b ‐ 16b) have been prepared by the Mannich reaction of 2,6‐disubstituted phenols with the corresponding N,N'‐dimethoxymethyldiaza‐crown ethers in benzene. The crystal structures of the diaza‐18‐crown‐6 ethers having iso‐propyl (10b) , tert‐butyl (11b) , and mixed methyl and tert‐butyl groups (12b) at positions 3′ and 5′ of the phenolic side arms were determined using X‐ray diffraction methods. Competitive transport by these ligands for sodium, potassium and cesium cations were measured under basic‐source phase and acidic‐receiving phase conditions.     

Non‐Shrinking Networked Materials from the Cross‐Linking Copolymerization of Spiroorthocarbonate with Bifunctional Oxetane

Summary: The cationic ring‐opening copolymerization behavior of SOC1 with BOXT and the properties of the obtained cross‐linked copolymers are described. SOC1 and BOXT are cationically copolymerized under various feed ratios to obtain the corresponding cross‐linked copolymers in 73–96% yields. The volume change during copolymerization could be controlled by the addition of SOC1 to obtain non‐shrinking or volume‐expanding copolymers. The glass transition temperatures (T_g) of the copolymers also decrease linearly with the feed ratio of SOC1, which suggests that the introduction of the flexible poly(SOC1) segment into the rigid BOXT cross‐linked segment relieves the internal stress in the resins that severely degrade their mechanical properties.

Cationic copolymerization of SOC1 and BOXT.     

Characterization of photoresists for ArF‐excimer laser lithography using monoenergetic positron beams

The volume and depth distributions of open spaces in photoresist films designed for ArF‐excimer laser light exposure were studied with monoenergetic positron beams. We measured the Doppler broadening spectra of the annihilation radiation and lifetime spectra of positrons for acrylate and cyclic olefin‐co‐maleic anhydride (COMA) polymers spin‐coated onto Si wafers with methyl amyl ketone, cyclohexanone, and propylene glycol methyl ether acetate solvents. The volume of open spaces in both prebaked acrylate and COMA films was estimated to be 0.12 nm³. The volume of open spaces in acrylate films decreased up to 20% by postexposure baking, but no large change was observed for COMA films. The decrease in the open volume was attributed to the removal of large molecules (adamantyl) from flexible main chains after the chemically amplified reaction of acrylate. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 341–346, 2004     

Synthesis of the racemic and optically active forms of gizzerosine,the inducer of gizzard erosion in chicks

The racemate and both the (R)- and (S)-forms of gizzerosine [2-amino-9-(4-imidazolyl)-7-azanonanoic acid] were synthesised, and the (S)-isomer was identified as the toxic substance in fish meal causing severe gizzard erosion (black vomit) in chicks.     

Polynomial time perfect sampling algorithm for two‐rowed contingency tables

This paper proposes a polynomial time perfect (exact) sampling algorithm for 2 × n contingency tables. The algorithm is based on monotone coupling from the past (monotone CFTP) algorithm. The expected running time is bounded by O(n³ lnN) where n is the number of columns and N is the total sum of all entries. © 2005 Wiley Periodicals, Inc. Random Struct. Alg., 2006     

An efficient diastereoselective synthesis of 6-hydroxy-4a-[3,4-crowned(15-crown-5)phenyl]-trans-decahydroisoquinoline

A high diastereoselective synthesis of 6-hydroxy-4a-aryl-$\text{trans}$-decahydroisoquinoline derivatives was achieved by an application of N-acyliminium ion-induced polyene cyclization procedure.