Novel nucleophilic C?C bond‐forming tele‐reaction of imidazole ring

Reaction of 2‐(1‐chloro‐2,2‐dimethylpropyl)‐1‐methyl‐1H‐irnidazoles with diethyl methylmalonate in the presence of NaH gave a normal S_N product, 2‐[(1,1‐diethoxycarbonylethyl)‐2,2‐dimethylpropyl]‐1‐methyl‐1H‐imidazole (2a) , and two tele‐reaction products, 5‐(1,1‐diethoxycarbonylethyl)‐1‐methyl‐2‐(2,2‐dimethylpropyl)‐1H‐imidazole (3a) and trans‐4,5‐di‐(1,1‐diethoxycarbonylethyl)‐4,5‐dihydro‐1‐methyl‐2‐(2,2‐dimethylpropyl)‐1H‐imidazole (4a) in 5, 17 and 70% yields, respectively. The scope and mechanism of this reaction are discussed.     

Efficient photocurrent generation by self-assembled monolayers composed of 3 10-helical peptides carrying linearly spaced naphthyl groups at the side chains

Self-assembled monolayers (SAMs) were prepared on a gold substrate from a 310-helical peptide carrying three naphthyl groups at the side chain (SSN3B) or from the reference peptides carrying no or one naphthyl group. The 310-helical conformation of SSN3B in solution was confirmed by 1H NMR spectroscopy and geometry optimization. Cyclic voltammetry and infrared absorption-reflection spectroscopy showed vertical molecular orientation and a well-packed structure in the SSN3B SAM. Anodic photocurrent was successfully generated by the SSN3B SAM in the presence of triethanolamine, and the current intensity was found to be much larger than those by the other SAMs from peptides carrying one naphthyl group. It was therefore concluded that the linearly spaced naphthyl groups along the helical axis act as photosensitizer and electron-hopping site to promote photocurrent generation remarkably.     

Furopyridines. xvi. Photo[2+2]cycloaddition of furo-[3,2-c]pyridin-4(5H)-one with acrylonitrile

The photocycloaddition of furo[3,2-c]pyridin-4(5H)-one (1) and its N-methyl derivative (1-Me) to acrylonitrile has been studied. The structures of the photoadducts isolated by column chromatography were determined on the basis of the nuclear magnetic resonance spectroscopy. The cycloaddition of 1 afforded an adduct 2 at the carbonyl oxygen and four possible isomers 3a, 3b, 3c and 3d of cyclobutane-fused adduct at the 6- and 7-position of 1 , and the addition of 1-Me the N-methyl derivatives 3a-Me, 3b-Me, 3c-Me and 3d-Me.     

Novel stereoconvergent transformation of 1,2a-disubstituted 1,2,2a,8b-tetrahydro-3H-benzo[b]cyclobuta[d]pyran-3-ones to 1,3-disubstituted 1,2,4a,9b-tetrahydrodibenzofuran-4-ols and its application to the second-generation synthesis of (+/-)-linderol A

1,2a-Disubstituted 1,2,2a,8b-tetrahydro-3H-benzo[b]cyclobuta[d]pyran-3-ones bearing an electron-withdrawing group at the 2a-position were treated with two equivalents of dimethylsulfoxonium methylide to give r-1,t-4a,t-9b-1,3-disubstituted 1,2,4a,9b-tetrahydrodibenzofuran-4-ols stereoconvergently regardless of the stereochemistry of the 1-position on the benzocyclobutapyran ring. This methodology was applied to the second-generation synthesis of (+/-)-linderol A, a melanin biosynthesis inhibitory natural product.     

Preparation of 2-, 3-, 4- and 7-(2-alkylcarbamoyl-1-alkylvinyl)benzo[b]furans and their BLT1 and/or BLT2 inhibitory activities

Several 2-alkylcarbamoyl-1-alkylvinylbenzo[b]furans were designed to find a selective leukotriene B4 (LTB4) receptor antagonist. 2-(2-Alkylcarbamoyl-1-alkylvinyl)benzo[b]furans having a substituent group at the 3-position, 4-(2-alkylcarbamoyl-1-methylvinyl)benzo[b]furans having a substituent group at the 3-position, and 7-(2-alkylcarbamoyl-1-methylvinyl)benzo[b]furans and 3-(2-alkylcarbamoyl-1-alkylvinyl)benzo[b]furans were prepared and evaluated for LTB4 receptor (BLT1 and BLT2) inhibitory activities. (E)-3-Amino-4-[2-[2-(3,4-dimethoxyphenyl)ethylcarbamoyl]-1-methylvinyl]benzo[b]furan ((E)-17c) showed potent and selective inhibitory activity for BLT2. On the other hand, (E)-7-(2-diethylcarbamoyl-1-methylvinyl)benzo[b]furan ((E)-27a) showed potent inhibitory activity for both BLT1 and BLT2.     

Furopyridines. XXVI. Reactions of cyanopyridine derivatives of furo[2,3‐b]‐, ‐[3,2‐b]‐, ‐[2,3‐c]‐ and ‐[3,2‐c]pyridine

Bromination of α‐cyanopyridine derivatives of furopyridines 1a‐d gave the 2,3‐dibromo‐2,3‐dihydro compounds 2a‐d in excellent yields. Treatment of 2a‐d with sodium hydroxide in methanol yielded compounds formed through the dehydrobromination and solvolysis of the nitrile. N‐Oxidation of 1a and 1b gave N‐oxide in much poor yield, while 1c and 1d gave the N‐oxide 13c and 13d in good yields. The nucleophilic reactions (cyanation, chlorination and acetoxylatoin) of 13c through a Reissert‐Henze type reaction gave poor results, which would be caused by the strong electron withdrawing effect of the cyano group.     

A Topological Proof of Stability of N-Front Solutions of the FitzHugh–Nagumo Equations

Consideration is devoted to traveling N-front wave solutions of the FitzHugh–Nagumo equations of the bistable type. Especially, stability of the N-front wave is proven. In the proof, the eigenvalue problem for the N-front wave bifurcating from coexisting simple front and back waves is regarded as a bifurcation problem for projectivised eigenvalue equations, and a topological index is employed to detect eigenvalues.     

Furopyridines. XVIII. Photocycloaddition of furo[2,3-c]pyridin-7(6H)-one with acrylonitrile

The photocycloaddition of furo[2,3-c]pyridin-7(6H)-one ( 1 ) and its N-mefhyl derivative ( 1-Me ) to acrylonitrile has been studied. The structures of the photoadducts isolated by colum chromatography were determined by the nuclear magnetic resonance spectroscopy and single crystal X-ray analysis. The cyclo-addition of 1 afforded an adduct 2 at the carbonyl oxygen and 8-cyano-8,9-dihydrofuro[d]azocin-7(6H)-one ( 3 ), and the addition of 1-Me the N-methyl derivative 3-Me of 3 , (9S*)-9-cyano-6-methyl-3a,7a-dihydro-3a,7a-ethanofuro[2,3-c]pyridin-7(6H)-one ( 4 ), (2S*, 2aR*, 7bR*)- ( 5 ) and (1R*, 2aS*, 7bS*)-2-cyano-3-methyl-4-oxo-1,2,2a,3,4,7b-hexahydrocyclobuta[e]furo[2,3-c]pyridine ( 6 ).