Search PubMed⌕ Search

Biomedical subjects

Chao-Jun Li

Publications and source records attributed to Chao-Jun Li.

50 records · Page 3Linked to original sources
PubMed2003

A highly efficient three-component coupling of aldehyde, alkyne, and amines via C-H activation catalyzed by gold in water.

A highly efficient three-component-coupling of aldehyde, alkyne, and amine (A3 Coupling) catalyzed by gold via C-H activation was developed in water. The reaction is general, and nearly quantitative yields of the corresponding propargylamines were obtained in most cases. Both aromatic and aliphatic aldehydes and amines can be used for the reaction. No additional cocatalyst or activator is required. A mechanistic rationale for the reaction has been proposed.

Journal Article↗
PubMed2003

The Barbier-Grignard-type carbonyl alkylation using unactivated alkyl halides in water.

The aqueous Barbier-Grignard-type alkylation of aldehydes with unactivated alkyl iodides and bromides was developed. By using a combination of zinc and cuprous iodide, catalyzed by indium(I) chloride, we successfully added tertiary, secondary, and primary alkyl halides to various aromatic aldehydes in 0.07 M aqueous Na2C2O4. A mechanistic rationale for the success of the reaction has been proposed.

Journal Article↗
PubMed2002

InCl(3)-catalyzed domino reaction of aromatic amines with cyclic enol ethers in water: a highly efficient synthesis of new 1,2,3,4-tetrahydroquinoline derivatives.

The tetrahydroquinoline moiety is a structural feature of many natural products. By using a domino reaction of aromatic amines and cyclic enol ethers or 2-hydroxy cyclic ether catalyzed by indium chloride in water, various tetrahydroquinoline derivatives were synthesized efficiently. Most cyclization products showed cis selectivity. The use of 2,3-dihydrofuran as the cyclic enol ether provided both higher reactivity and cis selectivity than the use of 3,4-dihydro-2H-pyran. The cis selectivity was tentatively rationalized due to chelation control in water.

Aniline Compounds↗
PubMed2002

Quasi-nature catalysis: developing C-C bond formations catalyzed by late transition metals in air and water.

This Account outlines the recent efforts of developing catalysis under the ambient conditions of air and water for synthetic purposes from the author's laboratory. The discussions are focused on catalytic reactions (mostly C-C bond formations) other than oxidations via late transition metals. It includes the following aspects: (1) copper-catalyzed C-C bond formations; (2) palladium-catalyzed C-C bond formations; (3) rhodium-catalyzed C-C bond formations; (4) ruthenium-catalyzed olefin isomerizations and C-H activations. The mechanism, limitations, and synthetic applications of these reactions are also discussed.

Air↗
PubMed1999

Magnesium-Mediated Carbon-Carbon Bond Formation in Aqueous Media: Barbier-Grignard Allylation and Pinacol Coupling of Aldehydes.

Magnesium-mediated Barbier-Grignard type alkylation of aldehydes with alkyl halides was studied in aqueous media. The reaction of aromatic aldehydes with allyl halides is highly effective with either THF or water as the reaction solvent but poor in a mixture of THF/water. It was found that the magnesium-mediated allylation of aldehydes with allyl bromide and iodide proceeds effectively in aqueous 0.1 N HCl or 0.1 N NH(4)Cl. Aromatic aldehydes reacted chemoselectively in the presence of aliphatic aldehydes. An exclusive selectivity was also observed when both aliphatic and aromatic aldehyde functionalities are present in the same molecule. In the absence of allyl halides, aldehydes and ketones reacted with magnesium in aqueous 0.1 N NH(4)Cl to form the corresponding pinacol coupling products in high yields. The effectiveness of the pinacol reaction was strongly influenced by the steric environment surrounding the carbonyl group. Aliphatic aldehydes and simple alkyl halides appear inert under the reaction conditions for either alkylation or the pinacol coupling reaction.

Journal Article↗
PubMed1998

Manganese-Mediated Carbon-Carbon Bond Formation in Aqueous Media: Chemoselective Allylation and Pinacol Coupling of Aryl Aldehydes.

The use of manganese as a mediator for allylations and pinacol couplings in aqueous media was investigated. The combination of manganese and copper is found to be a highly effective mediator for the allylation of aryl aldehydes in water. Such a combination is found to be more reactive than other previously reported metals in aqueous media. No reaction was observed with either manganese or copper alone as the mediator. Only a catalytic amount of copper is required for the proceeding of the reaction. The uses of Cu(0), Cu(I), and Cu(II) as the copper source are all effective. The use of a catalytic amount of manganese combined with a stoichoimetric amount of copper led to the failure of the reaction. Allyl chloride is found to be more effective than allyl bromide for the corresponding reaction. The use of substituted allyl halides gave a mixture of regio- and diastereoisomers. Aromatic aldehydes reacted chemoselectively in the presence of aliphatic aldehydes. An exclusive selectivity was also observed when both an aliphatic and an aromatic aldehyde functionalities are present in the same molecule. In the presence of acetic acid or ammonium chloride, manganese was found to effect the pinacol-coupling reaction in water. The reaction proceeds selectively with aryl aldehydes.

Journal Article↗
PubMed1998

Regio- and Diastereoselective Allenylation of Aldehydes in Aqueous Media: Total Synthesis of (+)-Goniofufurone(1).

The regio- and diastereoselectivities of metal-mediated allenylation of carbonyl compounds were investigated in aqueous media. Different metal mediators showed varied regioselectivities on product formation during propargylation-allenylation reactions of carbonyl compounds with simple propargyl bromide. Under the standard reaction conditions, the use of indium provided the highest regioselectivity, with a preference of formation of the homopropargyl alcohol. The use of tin and bismuth as the metal mediator provided slightly lower selectivities with the same preference. The use of zinc and cadmium as the mediators further lowered the product selectivity. The reactions of an aliphatic aldehyde with simple propargyl bromide showed a lower selectivity than the reaction of an aromatic aldehyde in most cases, except for the use of tin or zinc (where comparable selectivities were observed). On the other hand, the reaction of terminal-substituted propargyl bromides with aldehydes mediated by indium showed a high regioselectivity in forming allenylation products. The indium-mediated allenylation of carbonyl compounds bearing an alpha-hydroxyl group also proceeded with a high diastereoselectivity, forming syn-diols predominantly in aqueous ethanol. The high diastereoselectivity in allenylation of alpha-hydroxyl-substituted aldehydes was attributed to the chelation effect exhibited by the alpha-hydroxyl substitutent. Through the use of this highly diastereoselective allenylation, (+)-goniofufurone was synthesized from D-glucurono-6,3-lactone.

Journal Article↗