Production of Piperidine and δ‐Lactam Chemicals from Biomass‐Derived Triacetic Acid Lactone. (14th May 2021)

• Record Type: Journal Article
• Authors: Chen, Bingfeng; Xie, Zhenbing; Peng, Fangfang; Li, Shaopeng; Yang, Junjuan; Wu, Tianbin; Fan, Honglei; Zhang, Zhaofu; Hou, Minqiang; Li, Shumu; Liu, Huizhen; Han, Buxing
• Is Part Of: Angewandte Chemie. Volume 133:Number 26(2021)
• Page Start: 14526
• Page End: 14530
• Publication Date: 2021-05-14
• Subjects: biomass conversion -- N-heterocycle -- sustainable chemistry -- tandem catalysis -- zeolites; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202102353
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Piperidine and δ‐Lactam chemicals have wide application, which are currently produced from fossil resource in industry. Production of this kind of chemicals from lignocellulosic biomass is of great importance, but is challenging and the reported routes give low yield. Herein, we demonstrate the strategy to synthesize 2‐methyl piperidine (MP ) and 6‐methylpiperidin‐2‐one (MPO ) from biomass‐derived triacetic acid lactone (TAL ) that is produced microbially from glucose. In this route, TAL was firstly converted into 4‐hydroxy‐6‐methylpyridin‐2(1 H )‐one (HMPO ) through facile aminolysis, subsequently HMPO was selectively transformed into MP or MPO over Ru catalysts supported on beta zeolite (Ru/BEA‐X, X is the molar ratio of Si to Al) via the tandem reaction. It was found that the yield of MP could reach 76.5 % over Ru/BEA‐60 in t ‐BuOH, and the yield of MPO could be 78.5 % in dioxane. Systematic studies reveal that the excellent catalytic performance of Ru/BEA‐60 was closely correlated with the cooperative effects between active metal and acidic zeolite with large pore geometries. The related reaction pathway was studied on the basis of control experiments. Abstract : A novel tandem catalytic route was developed for the selective production of 2‐methyl piperidine (MP ) or 6‐methylpiperidin‐2‐one (MPO ) from biomass‐derived triacetic acid lactone (TAL ), which opens the way for efficient production of piperidine and δ‐lactam chemicals from renewable biomass.