Regioselectivity in palladium-indium iodide-mediated allylation reaction of glyoxylic oxime ether and N-sulfonylimine

Allylation reaction of electron-deficient imines with allylic alcohol derivatives in the presence of a catalytic amount of palladium(0) complex and indium(I) iodide was studied. The reversibility of allylation was observed in the reaction of glyoxylic oxime ether having camphorsultam. As the important effect of water on regioselectivity, the gamma-adducts were kinetically formed from monosubstituted allylic reagents in the presence of water. The selective formation of thermodynamically stable alpha-adducts was observed in anhydrous THF. In contrast, the allylation of N-sulfonylimine gave the gamma-adducts with high regioselectivities even under anhydrous reaction conditions.     

Asymmetric synthesis of alpha-amino acids: indium-mediated reactions of glyoxylic oxime ether in aqueous media

The indium-mediated allylation and alkylation reactions of the Oppolzer camphorsultam derivative of glyoxylic oxime ether proceeded with excellent diastereoselectivity in aqueous media, providing a variety of enantiomerically pure alpha-amino acids.     

Stannyl radical addition-cyclization of oxime ethers connected with olefins

Stannyl radical addition-cyclization of oxime ethers connected with olefin moieties was studied. The radical reactions proceeded effectively by the use of triethylborane as a radical initiator to provide the functionalized pyrrolidines via a carbon-carbon bond-forming process.     

Enantioselectively catalyzed oxidation of 3,4-dihydroxy-l-phenylalanine by N-lauroyl L or D-histidine-Cu(II) complex in CTABr micelles.

In order to investigate the enzyme model reaction the oxidation of 3,4-dihydihydroxy-L-phenylalanine(L-DOPA) was carried out using optically active catalyst, N-lauroyl L or D-histidine-Cu(II) complex(L or D-LauHis-Cu(II)), showing appreciable enantioselectivity in the presence of the mixed micelles with CTABr.     

Single-bubble sonochemiluminescence in aqueous luminol solutions

Sonochemiluminescence (SCL) of luminol due to a single bubble is studied through spectral measurement. No SCL was observed from a stable single bubble that emitted high-intensity sonoluminescence (SL). In contrast, SCL was observed under conditions of an unstable dancing bubble, where a bubble grows and ejects tiny bubbles, making it "dance" by counteraction. Furthermore, SCL was observed from dancing bubbles even when SL was not observed, depending on the dissolved gas content. The instability of bubble collapse is the key parameter governing SCL.     

Double bond isomerization of 5-vinylbicyclo[2.2.1]hept-2-ene to 5-ethylidenebicyclo[2.2.1]hept-2-ene over alkaline earth oxides

All the alkaline earth oxides exhibit activities for double, bond isomerization of 5-vinylbicyclo[2.2.1]hept-2-ene (VBH) to 5-ethylidenebicyclo[2.2.1]hept-2-ene (EBH) at a reaction temperature of 273 K. The order of the activity on the basis of unit weight of catalyst was CaO>MgO>SrO>BaO when compared under optimum pretreatment conditions. The E/Z ratio in the products is determined by the reaction temperature regardless of the type of catalyst; the ratios were 82/18 and 88/12 for the reaction temperatures of 323 and 273 K, respectively.     

Synthesis and Rearrangement of P‐Nitroxyl‐Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study

Low‐temperature generation of P‐nitroxyl phosphane 2 (Ph₂POTEMP), which was obtained by the reaction of Ph₂PH ( 1 ) with two equivalents of TEMPO, is presented. Upon warming, phosphane 2 decomposed to give P‐nitroxyl phosphane P‐oxide 3 (Ph₂P(O)OTEMP) as one of the final products. This facile synthetic protocol also enabled access to P‐sulfide and P‐borane derivatives 7 and 13 , respectively, by using Ph₂P(S)H ( 6 ) or Ph₂P(BH₃)H ( 11 ) and TEMPO. Phosphane sulfide 7 revealed a rearrangement to phosphane oxide 8 (Ph₂P(O)STEMP) in CDCl₃ at ambient temperature, whereas in THF, thermal decomposition of sulfide 7 yielded salt 10 ([TEMP‐H₂][Ph₂P(S)O]). As well as EPR and detailed NMR kinetic studies, indepth theoretical studies provided an insight into the reaction pathways and spin‐density distributions of the reactive intermediates.     

Enormously extended π-electronic conjugation system of dimeric octaethylporphyrin transmitted with anthracene

Based on the fact that anthracene (Anth) possesses much higher similarity in electron-releasing ability to porphyrin nucleus than the other polyacenes, the dimeric octaethylporphyrin (OEP) derivatives 4 and 5 (OEP–Anth–OEP) were synthesized and their structure–property relationships were examined, as compared with related OEP dimers 1–3. Among them, the derivative 4 showed enormously high electronic communication between two terminal OEP rings, potentially providing a suitable unit of the electronic structure for molecular design of the OEP devices operating with less energy and with higher sensitivity to outside stimuli.