1,3-Diene architectures are not only widely present in natural products, pharmaceuticals, and functional organic materials but also serve as versatile building blocks to furnish important functionalized molecules in s...1,3-Diene architectures are not only widely present in natural products, pharmaceuticals, and functional organic materials but also serve as versatile building blocks to furnish important functionalized molecules in synthetic chemistry due to conjugated repeating C=C units. Accordingly, various strategies to access substituted 1,3-dienes in a stereoselective manner have been developed. However, chemo-, regio-and stereoselective synthesis of highly substituted 1,3-dienes still remains elusive and challenging. Readily available propargylic esters have emerged as an appealing class of synthetic intermediates for accessing functionalized 1,3-dienes, especially challenging tri-or tetrasubstituted variants, via transition-metal catalysis, including electrophilic metal and redox neutral catalysis. This review, for the first time, systematically highlights recent advances in transitionmetal catalyzed synthesis of substituted 1,3-dienes from propargylic esters, discusses the mechanisms and synthetic utilities, and gives the remaining challenges and potential opportunities in this field.展开更多
The dilute sulfuric acid pretreatment of lignocellulosic biomass is a well understood process that significantly enhances the yield of glucose after enzymatic saccharification.The goal of this research was to perform ...The dilute sulfuric acid pretreatment of lignocellulosic biomass is a well understood process that significantly enhances the yield of glucose after enzymatic saccharification.The goal of this research was to perform a systematic study to evaluate the yield of fermentable sugars during dilute sulfuric acid pretreatment that is co-catalyzed with the transition metal Lewis acid salts:AlCl_(3),FeCl_(2),FeCl_(3),and La(OTf)_(3).All Lewis acids apart from FeCl_(2)reduced the presence of xylo-oligomers by a large margin when compared to the non-co-catalyzed control sample pretreatments.The presence of these xylo-oligomers acts as inhibitors during enzymatic saccaharification step.The Lewis acids AlCl_(3),FeCl_(3),and La(OTf)_(3)were also able to marginally increase the overall enzymatic digestibility specifically for corn stover pretreated at 160℃with 10 mM of Lewis acids.The hard Lewis acid such as AlCl3 increased the formation inhibitory products such as furfural and 5-hydroxymethylfurfural(HMF).There was good correlation between reduction of xylo-oligomers and increased concentration furfural with increase in Lewis acid hardness.展开更多
受阻Lewis酸碱对(Frustrated Lewis Pairs,FLPs)是一类具有特殊反应活性的Lewis酸碱对。自发现以来,FLPs受到了广泛关注并在许多领域崭露头角。本文对FLPs在不对称氢化、高分子聚合、CO_2催化还原等应用领域取得的突破进行了介绍;同时...受阻Lewis酸碱对(Frustrated Lewis Pairs,FLPs)是一类具有特殊反应活性的Lewis酸碱对。自发现以来,FLPs受到了广泛关注并在许多领域崭露头角。本文对FLPs在不对称氢化、高分子聚合、CO_2催化还原等应用领域取得的突破进行了介绍;同时对过渡金属FLPs和FLPs配位的过渡金属催化体系进行了综述;最后对FLPs领域未来的发展前景进行了展望。展开更多
基金supported by the National Natural Science Foundation of China (22071111)the Jiangsu Specially Appointed Professor Plan+1 种基金the Natural Science Foundation of Jiangsu Province(BK20201368, BK20220409)the Postgraduate Research&Practice Innovation Program of Jiangsu Province (KYCX23_1683)。
文摘1,3-Diene architectures are not only widely present in natural products, pharmaceuticals, and functional organic materials but also serve as versatile building blocks to furnish important functionalized molecules in synthetic chemistry due to conjugated repeating C=C units. Accordingly, various strategies to access substituted 1,3-dienes in a stereoselective manner have been developed. However, chemo-, regio-and stereoselective synthesis of highly substituted 1,3-dienes still remains elusive and challenging. Readily available propargylic esters have emerged as an appealing class of synthetic intermediates for accessing functionalized 1,3-dienes, especially challenging tri-or tetrasubstituted variants, via transition-metal catalysis, including electrophilic metal and redox neutral catalysis. This review, for the first time, systematically highlights recent advances in transitionmetal catalyzed synthesis of substituted 1,3-dienes from propargylic esters, discusses the mechanisms and synthetic utilities, and gives the remaining challenges and potential opportunities in this field.
基金This study was financially supported by National Renewable Energy Laboratory Subcontract No.AEV-0-40634-01North Dakota Experimental Program to Stimulate Competitive Research(EPSCoR).
文摘The dilute sulfuric acid pretreatment of lignocellulosic biomass is a well understood process that significantly enhances the yield of glucose after enzymatic saccharification.The goal of this research was to perform a systematic study to evaluate the yield of fermentable sugars during dilute sulfuric acid pretreatment that is co-catalyzed with the transition metal Lewis acid salts:AlCl_(3),FeCl_(2),FeCl_(3),and La(OTf)_(3).All Lewis acids apart from FeCl_(2)reduced the presence of xylo-oligomers by a large margin when compared to the non-co-catalyzed control sample pretreatments.The presence of these xylo-oligomers acts as inhibitors during enzymatic saccaharification step.The Lewis acids AlCl_(3),FeCl_(3),and La(OTf)_(3)were also able to marginally increase the overall enzymatic digestibility specifically for corn stover pretreated at 160℃with 10 mM of Lewis acids.The hard Lewis acid such as AlCl3 increased the formation inhibitory products such as furfural and 5-hydroxymethylfurfural(HMF).There was good correlation between reduction of xylo-oligomers and increased concentration furfural with increase in Lewis acid hardness.
基金Project supported by the National Natural Science Foundation of China(Nos.21673301,21473261,21502023)the Guangdong Natural Science Funds for Distinguished Young Scholar(No.2015A030306027)~~
文摘受阻Lewis酸碱对(Frustrated Lewis Pairs,FLPs)是一类具有特殊反应活性的Lewis酸碱对。自发现以来,FLPs受到了广泛关注并在许多领域崭露头角。本文对FLPs在不对称氢化、高分子聚合、CO_2催化还原等应用领域取得的突破进行了介绍;同时对过渡金属FLPs和FLPs配位的过渡金属催化体系进行了综述;最后对FLPs领域未来的发展前景进行了展望。
