Zhi-Liang Shen

Enantioselective Cationic Polyene Cyclization vs Enantioselective Intramolecular Carbonyl−Ene Reaction

This paper describes highly efficient catalytic enantioselective cationic polyene cyclization and catalytic enantioselective intramolecular carbonyl-ene reaction in good to high yields with high enantioselectivities. The intimate relationship and mechanistic differences between the two enantioselective reactions were studied in detail. In addition, the cyclization products are versatile and useful building blocks for natural products and pharmaceuticals syntheses.

Synthesis of water-tolerant indium homoenolate in aqueous media and its application in the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling with acid chloride.

The first water-tolerant, ketone-type indium homoenolate was synthesized via the oxidative addition of In/InCl(3) to enones. The reaction proceeds exclusively in aqueous media. Both indium and indium(III) chloride are necessary for the smooth conversion of the reaction. Similar results were obtained when InCl or InCl(2) was used in place of In/InCl(3). The synthetic utility of the indium homoenolate was demonstrated through the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling of indium homoenolate with acid chloride.

One-pot chemoenzymatic syntheses of enantiomerically-enriched O-acetyl cyanohydrins from aldehydes in ionic liquid

A practical and efficient method for the synthesis of optically active O-acetyl cyanohydrins via one-pot lipase-catalyzed kinetic resolution of the in situ generated racemic cyanohydrins or O-acetyl cyanohydrins using an ionic liquid as both reaction media and promoter has been described.

Indium-copper and indium-silver mediated barbier-grignard-type alkylation reaction of aldehydes using unactivated alkyl halides in water.

An efficient method has been developed for the Barbier-Grignard-type alkylation reaction of aldehydes (including aliphatic version) using unactivated alkyl halides in water in the presence of an In/CuI/I(2) or In/AgI/I(2) system. The reactions proceeded more efficiently in water than in organic solvent. In, CuI or AgI, and I(2) were all essential for the efficient progress of the reactions. A radical-type reaction mechanism was studied and proposed by using 4-pentenal as substrate.

Synthesis and application of a recyclable ionic liquid-supported imidazolidinone catalyst in enantioselective 1,3-dipolar cycloaddition

The synthesis of recyclable ionic liquid-supported imidazolidinone catalyst I and its application in 1,3-dipolar cycloaddition of nitrone with α,β-unsaturated aldehyde with high performance were described. Most importantly, the catalyst I can be recovered and recycled for up to five runs without observing significant decrease in catalytic activity.

Application of recyclable ionic liquid-supported imidazolidinone catalyst in enantioselective Diels–Alder reactions

The application of ionic liquid-supported imidazolidinone catalyst I in enantioselective Diels–Alder reactions was investigated. The Diels–Alder reactions involving α,β-unsaturated aldehydes and cyclopentadiene proceeded efficiently in the presence of catalyst I to provide the desired products in moderate to good yields with good to excellent enantioselectivities. Especially noteworthy, catalyst I can be recovered and reused for up to five runs while maintaining its high catalytic activity.

Synthesis of 3‐Oxaterpenoids and Its Application in the Total Synthesis of (±)‐Moluccanic Acid Methyl Ester

Cascades: An InBr(3)-catalyzed intermolecular polyene cyclization initiated by a Prins reaction provides a concise approach to 3-oxaterpenoid derivatives. The reaction is compatible with various aldehydes, ketones, and polyolefin-alcohol substrates. In addition, the total synthesis of (±)-moluccanic acid methyl ester was achieved in seven steps by using such a Prins-polyene cyclization as the key step.

Palladium-catalyzed cross-coupling of indium homoenolate with aryl halide with wide functional group compatibility.

An efficient palladium-catalyzed cross-coupling of indium homoenolate with aryl halide is described. The reactions proceeded efficiently in DMA at 100 °C to afford the desired products of β-aryl ketones in moderate to good yields. Various important functional groups including COR, COOR, CHO, CN, OH, and NO(2) can be well tolerated in the protocol.

Zn/InCl3-Mediated Pinacol Cross-Coupling Reactions of Aldehydes with α,β-Unsaturated Ketones in Aqueous Media

A zinc/indium chloride-mediated pinacol cross-coupling reaction between aldehyde and alpha,beta-unsaturated ketone in aqueous media was developed. The 1,2-diols were obtained in moderate to good yields with up to 93:7 diastereoselectivity.

Direct synthesis of ester-containing indium homoenolate and its application in palladium-catalyzed cross-coupling with aryl halide

An efficient method for the synthesis of ester-containing indium homoenolate via a direct insertion of indium into β-halo ester in the presence of CuI/LiCl was described. The synthetic utility of the indium homoenolate was demonstrated by palladium-catalyzed cross-coupling with aryl halides in DMA with wide functional group compatibility.