Chinese Academy of Sciences

Fudan University

East China Normal University

Shengming Ma

Juntao Ye

Yu Liu

Kai Chen

Qi Liu

Jiajia Cheng

Baoqiang Wan

Suhua Li

Haibo Xu

Shichao Yu

Yuli Wang

Hui Qian

Jinqiang Kuang

Qiong Yu

Weifeng Zheng

Jinxian Liu

Weiming Yuan

The present invention discloses a phosphine nitrogen ligand with multiple chiral centers and its synthesis method and application. The ligand has the axial chirality of a biaryl skeleton and the central chirality of a chiral amine. The chiral ligand is synthesized from commercially available raw materials through a simple five-step reaction, and the resulting diastereomer can be separated by simple column chromatography or recrystallization. The chiral phosphine nitrogen ligand synthesized by the present invention can catalyze the asymmetric three-component coupling reaction of terminal alkynes, aldehydes and amines, and realize the efficient preparation of chiral propargyl amines with high optical activity.

Class of phosphine nitrogen ligand with multiple chiral centers and its synthesis method and application

The present invention discloses a method for directly constructing highly optically active tetrasubstituted allenic acid compounds, i.e., a one-step process for directly constructing highly optically active axially chiral tetrasubstituted allenic acid compounds by using tertiary propargyl alcohol, carbon monoxide and water as reactants in an organic solvent in the presence of palladium catalyst, chiral diphosphine ligand, monophosphine ligand and organic phosphoric acid. The method of the present invention has the following advantages: operations are simple, raw materials and reagents are readily available, the reaction conditions are mild, the substrate has high universality, the functional group has good compatibility, and the reaction has high enantioselectivity (90%&#x2dc;&#x3e;99% ee). The highly optically active allenic acid compounds obtained by the present invention can be used as an important intermediate to construct &#x3b3;-butyrolactone compounds containing tetrasubstituted chiral quaternary carbon centers, tetrasubstituted allenic alcohol and other compounds.

Method for directly constructing highly optically active tetrasubstituted allenic acid compounds

The present invention relates to an optically active axially chiral &#x3b1;-allenic alcohol, a synthesis method and use thereof. The invention relates to a method of preparing a highly optically active chiral &#x3b1;-allenic alcohol by using propargyl alcohol, aldehyde and chiral &#x3b1;,&#x3b1;-diphenyl-L-prolinol under the protection of tert-butyldimethylsilyl with an accelerant zinc bromide. The axially chiral &#x3b1;-allenic alcohol has the structural formula (I). The method of the present invention has the following advantages: the synthesis route is short, operations are simple, raw materials are readily available, separation and purification are convenient, the substrate has high universality, the total yield is high, and enantioselectivity and diastereoselectivity are high. The highly optically active axially chiral &#x3b1;-allenic alcohol synthesized by the method of the present invention can conveniently synthesize 2,5-dihydrofuran compounds having central chirality and complete chirality, and at the same time can further synthesize axially chiral allenic amine and allenic malonic ester compounds having complete chirality. 

Optically active axially chiral alpha-allenic alcohol, synthesis method and use thereof

Provided is a process for producing aldehydes or ketones by oxidizing alcohols with oxygen, which comprises oxidizing alcohols to aldehydes or ketones in an organic solvent at room temperature with oxygen or air as an oxidant, wherein ferric nitrate (Fe(NO3)3.9H2O), 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) and an inorganic chloride are used as catalysts, the reaction time is 1-24 hours, and the molar ratio of said alcohols, 2,2,6,6-tetramethylpiperidine N-oxyl and the inorganic chloride is 100:1&#x2dc;10:1&#x2dc;10:1&#x2dc;10. The present process has the advantages of high yield, mild reaction conditions, simple operation, convenient separation and purification, recoverable solvents, substrates used therefor being various and no pollution, and therefore it is adaptable to industrialization.

Process for producing aldehydes or ketones by oxidizing alcohols with oxygen

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Shanghai, China

Shengming Ma