Ring-locking enables selective anhydrosugar synthesis from carbohydrate pyrolysis

doi:10.1039/c6gc01600f

	Ring-locking enables selective anhydrosugar synthesis from carbohydrate pyrolysis
	Zhang, Z. Conrad 3; Chen, Li 1; Zhao, Jinmo 2; Pradhan, Sivaram 1; Brinson, Bruce E.2; Scuseria, Gustavo E.2; Wong, Michael S.1,2,4,5
刊名	GREEN CHEMISTRY
	2016
卷号	18 期号:20 页码:5438-5447
ISSN号	1463-9262
DOI	10.1039/c6gc01600f
文献子类	Article
英文摘要	The selective production of platform chemicals from thermal conversion of biomass-derived carbohydrates is challenging. As precursors to natural products and drug molecules, anhydrosugars are difficult to synthesize from simple carbohydrates in large quantities without side products, due to various competing pathways during pyrolysis. Here we demonstrate that the nonselective chemistry of carbohydrate pyrolysis is substantially improved by alkoxy or phenoxy substitution at the anomeric carbon of glucose prior to thermal treatment. Through this ring-locking step, we found that the selectivity to 1,6-anhydro-beta-D-glucopyranose (levoglucosan, LGA) increased from 2% to greater than 90% after fast pyrolysis of the resulting sugar at 600 degrees C. DFT analysis indicated that LGA formation becomes the dominant reaction pathway when the substituent group inhibits the pyranose ring from opening and fragmenting into non-anhydrosugar products. LGA forms selectively when the activation barrier for ring-opening is significantly increased over that for 1,6-elimination, with both barriers affected by the substituent type and anomeric position. These findings introduce the ring-locking concept to sugar pyrolysis chemistry and suggest a chemical-thermal treatment approach for upgrading simple and complex carbohydrates.
WOS关键词	GLUCOSE PYROLYSIS ; CELLULOSE ; BIOMASS ; LEVOGLUCOSAN ; CONVERSION ; SUGARS ; FUELS ; CHEMICALS ; FRUCTOSE ; BIOFUELS
WOS研究方向	Chemistry
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000386213800005
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/169972]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Zhang, Z. Conrad; Wong, Michael S.
作者单位	1.Rice Univ, Dept Chem & Biomol Engn, Houston, TX 77005 USA 2.Rice Univ, Dept Chem, Houston, TX 77005 USA 3.Dalian Inst Chem Phys, Dalian Natl Lab Clean Energy, Dalian 116023, Liaoning, Peoples R China 4.Rice Univ, Dept Civil & Environm Engn, Houston, TX 77005 USA 5.Rice Univ, Dept Mat Sci & NanoEngn, Houston, TX 77005 USA
推荐引用方式 GB/T 7714	Zhang, Z. Conrad,Chen, Li,Zhao, Jinmo,et al. Ring-locking enables selective anhydrosugar synthesis from carbohydrate pyrolysis[J]. GREEN CHEMISTRY,2016,18(20):5438-5447.
APA	Zhang, Z. Conrad.,Chen, Li.,Zhao, Jinmo.,Pradhan, Sivaram.,Brinson, Bruce E..,...&Wong, Michael S..(2016).Ring-locking enables selective anhydrosugar synthesis from carbohydrate pyrolysis.GREEN CHEMISTRY,18(20),5438-5447.
MLA	Zhang, Z. Conrad,et al."Ring-locking enables selective anhydrosugar synthesis from carbohydrate pyrolysis".GREEN CHEMISTRY 18.20(2016):5438-5447.