Preparation method of substituted cis-olefin

Abstract

The invention belongs to the technical field of medicine and natural compound chemical intermediates and related chemistry, and relates to a preparation method of substituted cis-olefin. The method includes using alkyne and derivatives thereof as raw materials, a nanoporous gold catalyst as a catalyst, hydrogen gas as a hydrogen source and an organic alkali as a solvent, and performing selective hydrogenation to prepare cis-olefin, wherein hydrogen pressure is 0.1-20.0MPa; and molar concentration of alkyne and derivatives thereof in the solvent is 0.01-2mmol / mL. The catalyst is a nanoporous gold catalyst, the porous frame size is 5-50nm, and the molar ratio of alkyne and the derivatives thereof to the catalyst is 1:0.01-1:0.1. The method has the advantages of high product selectivity, and simple operation and post-treatment; and the catalyst is good in reproducibility, the catalytic effect is not significantly lowered after the catalyst is repeatedly used, which provides the possibility for industrialization.

Description

technical field [0001] The invention belongs to the field of chemical intermediates of medicine and natural compounds and related chemical technology, and relates to a preparation method of substituted cis-olefins. Background technique [0002] The selective reduction of alkynes to cis-alkenes is a very important step in organic synthesis, especially in the synthesis of some important high-value compounds (such as pheromones, industrial raw materials and other important natural products), the synthesis of high-purity cis-alkenes is the key. [0003] The traditional methods for preparing cis-alkenes by selective reduction of internal alkynes are mainly divided into two categories, one is homogeneous catalysts combining Pd, V, Nb and other transition metals with ligands, which have high activity and high selectivity However, these catalysts are expensive, difficult to separate and recover, and cannot be reused [HAUWERT P, MAESTRI G, SPRENGERS J W, ELSEVIER C J.Angew.Chem.Int....

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Problems solved by technology

[0003] The traditional methods for preparing cis-alkenes by selective reduction of internal alkynes are mainly divided into two categories, one is homogeneous catalysts combining Pd, V, Nb and other transition metals with ligands, which have high activity and high selectivity However, these catalysts are expensive, difficult to separate and recover, and cannot be reused [HAUWERT P, MAESTRI G, SPRENGERS J W, ELSEVIER C J.Angew.Chem.Int.Ed.2008,47(17):3223–3226 ; LA PIERRE H S, ARNOLD J, TOSTE F D.Angew.Chem.Int.Ed.2011, 50, 3900–3903; GIANETTI T L, TOMSON N C, ARNOLD J, BERGMAN R G.J.Am.Chem.Soc.2011, 133, 14904–14907.]; the second is heterogeneous catalysts that have been studied more, which mainly use transition metals such as Pd and Ni and H 2 Catalytic reduction, such as the famous Lindela catalyst and P2-Ni catalyst, but there are disadvantages of Z / E isomerization and excessive reduction to alkanes, such as Lindela catalyst requires complex devices and strict hydrogen control to prevent excessive reduction

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