Zinc chloride-catalyzed Grignard addition reaction of aromatic nitriles.

In the alkyl addition reaction of aromatic nitriles using Grignard reagents, ketones are formed after hydrolysis. However, this addition reaction is often slow compared to that using reactive organolithium(i) reagents. In this study, we improved the reaction by using zinc(ii)ates, which are generated using Grignard reagents and zinc chloride (ZnCl) as a catalyst.

Photocatalytic Addition Reactions of Ketene Silyl Acetals with Alkenes through Formation of α-Carbonyl Radicals.

Addition reactions of ketene silyl acetals with alkenes that do not have an electron-withdrawing group are generally difficult because the nucleophilicity of ketene silyl acetals and the electrophilicity of alkenes are not sufficient. Herein, we report photocatalytic addition reactions of ketene silyl acetals with alkenes that proceed through formation of α-carbonyl radicals. In the presence of an appropriate protic additive, the reactions proceeded smoothly under blue-light irradiation to afford the desired products in moderate to high yields.

α-Alkylation of Ketones with Alkenes Enabled by Photoinduced Activation of Silyl Enol Ethers in the Presence of a Small Amount of Water.

Under blue-light irradiation conditions with a photocatalyst [1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene], silyl enol ethers reacted with alkenes in the presence of a small amount of water to afford the α-alkylation products in good to high yields. A thiol cocatalyst was found to expand the substrate scope of the reaction.

Asymmetric C(sp)-H functionalization of unactivated alkylarenes such as toluene enabled by chiral Brønsted base catalysts.

Benzylic functionalisation of unactivated alkylarenes remains as a significant challenge in asymmetric catalysis due to their less reactive nature. Here, we show development of catalytic asymmetric C(sp)-H functionalization of unactivated alkylarenes such as toluene with imines. The reactions proceeded smoothly under proton-transfer conditions using a chiral, strong Brønsted base catalyst system.

Catalytic Direct-Type Addition Reactions of Alkylarenes with Imines and Alkenes.

Catalytic addition reactions of very weakly acidic nonactivated alkylarenes such as toluene and its derivatives were developed by using a strongly basic mixed catalyst system under mild reaction conditions. The addition reactions with imines and alkenes proceeded smoothly under proton-transfer conditions to afford the desired products in good to high yields, and high levels of regio- and stereoselectivity were achieved. It was also revealed that the asymmetric addition reaction of an alkylarene was possible.

[Colorectal carcinoma with hemiparesis due to isolated brain metastases as an initial symptom - a case report].

We present a rare case of colorectal carcinoma in which hemiparesis was the initial symptom. A 75-year-old woman presented with incomplete left-sided hemiparesis. Brain magnetic resonance imaging(MRI)revealed a 13-mm mass in the right frontal lobe; the mass was resected via craniotomy.

[Gallbladder cancer with elevated serum α-fetoprotein, α-fetoprotein-L3, and human chorionic gonadotropin levels].

A 61-year-old woman presented with fever and was diagnosed with choledocholithiasis, which was removed endoscopically. Incidentally, a markedly elevated serum α-fetoprotein(AFP)level was detected(1,951 ng/mL), but computed tomography( CT)showed only diffuse gallbladder wall thickening. Subsequently, markedly elevated serum AFP-L3 and human chorionic gonadotropin(HCG)levels were detected(99.