Alanine(Ala)-xylose(Xyl)Amadori compound(A-X-ARP)was found to increase the yields of 1-octen-3-ol and enals derived from linoleic acid oxidation,during the thermal processing of Agrocybe aegerita enzymatic hydrolysate...Alanine(Ala)-xylose(Xyl)Amadori compound(A-X-ARP)was found to increase the yields of 1-octen-3-ol and enals derived from linoleic acid oxidation,during the thermal processing of Agrocybe aegerita enzymatic hydrolysates(AEH).To elucidate the key intermediate contributing to this enhancement,model systems combining linoleic acid with A-X-ARP,Ala,and glyoxal(GO)were established,and the reaction products were analyzed.Ala,regenerated through the decomposition A-X-ARP,was identified as a crucial factor driving the production of enals and 1-octen-3-ol.Further thermal reaction models of linoleic acid with amino acids featuring diverse side chains revealed the universal catalytic effect of amino acids on enals and 1-octen-3-ol formation.Moreover,the amino group within amino acids was determined to be the key functional group responsible for this catalytic activity.Notably,the presence of amino acid was observed to reduce the oxygen dependence of linoleic acid oxidation in producing 1-octen-3-ol and enals.As a result,the addition of A-X-ARP during the thermal treatment of AEH increased the yield of 1-octen-3-ol,a compound with a typical mushroom-like note,from 19.3±3.7(OAV=19)to 71.4±9.8μg/L(OAV=71).These findings provided new insights for the development of mushroom-flavored seasonings.展开更多
Axially chiral molecules have been widely used in inorganic,material and medicinal chemistry.Compared with well-established N-heterocyclic carbene(NHC)-catalyzed asymmetric construction of centrally chiral molecules,N...Axially chiral molecules have been widely used in inorganic,material and medicinal chemistry.Compared with well-established N-heterocyclic carbene(NHC)-catalyzed asymmetric construction of centrally chiral molecules,NHC-catalyzed atroposelective synthesis of axially chiral molecules remains largely underdeveloped.Notably,alkynyl acyl azolium intermediates were commonly used in constructing a heteroaryl ring to furnish axially enantioenriched heteroaryl-aryls.The inherent character of the intermediates often led to react with sterically hindered substrates difficultly.Herein,we have successfully disclosed the atroposelective synthesis of axially chiral heteroaryl-aryls from sterically hindered enols through the use of chiral NHCs as catalysts for highly enantioselective Coates-Claisen rearrangements via catalytically generatedα,β-unsaturated acyl azoliums.This approach will enable the concise synthesis of valuable tetra-ortho-substituted 2-pyrones in one step with good yield and chirality control.展开更多
Lacebark pine （Pinus bungeana）, an evergreen conifer species native to China, is noted for its graceful profile. It has a height up to 30 m. Bark on young trees smooth, dull grey, scaling off in small patches like a...Lacebark pine （Pinus bungeana）, an evergreen conifer species native to China, is noted for its graceful profile. It has a height up to 30 m. Bark on young trees smooth, dull grey, scaling off in small patches like a plane tree, changing to chalky-white on old trunks, by which the species can be recognized from a long distance.展开更多
With the hypothesis of simple units integration to create new reactivities,a strategy for the synthesis of polyfunctionalized 5-alkenyl-3-carbonylfurans fromγ-hydroxyl enal and 1,3-dicarbonyl compounds is established...With the hypothesis of simple units integration to create new reactivities,a strategy for the synthesis of polyfunctionalized 5-alkenyl-3-carbonylfurans fromγ-hydroxyl enal and 1,3-dicarbonyl compounds is established,featuring readily available starting materials,high efficiency,good functional groups compatibility,green chemistry with high atom economy and only water release,etc.,to provide a series of polyfunctionalized 5-alkenyl-3-carbonylfurans,which could be applied to the late-stage functionalization of naturally occurring compounds and bioactive molecules,as well as the transformation to pyrroles and polycyclic aromatic hydrocarbon via electrocyclic reaction.Theγ-hydroxyl has played an important role in the unexpected process of ring opening isomerization of 2H-pyran to furanones,as confirmed by detailed mechanistic studies.展开更多
A mild and highly efficient amine-catalyzed, IBX-mediated oxidation of aldehydes to （E） selective a, β-unsamrated aldehydes has been achieved in good yields. The process features a new oxidation of enamines to imin...A mild and highly efficient amine-catalyzed, IBX-mediated oxidation of aldehydes to （E） selective a, β-unsamrated aldehydes has been achieved in good yields. The process features a new oxidation of enamines to iminium ions in a catalytic fashion.展开更多
基金supported by the National Natural Science Foun-dation of China 32172330Postgraduate Research&Practice Innova-tion Program of Jiangsu Province(KYCX23_2513)+2 种基金China Postdoctoral Science Foundation(2022M710176)“Collaborative innovation center of food safety and quality control in Jiangsu Province”the China Scholarship Council(202406790101).
文摘Alanine(Ala)-xylose(Xyl)Amadori compound(A-X-ARP)was found to increase the yields of 1-octen-3-ol and enals derived from linoleic acid oxidation,during the thermal processing of Agrocybe aegerita enzymatic hydrolysates(AEH).To elucidate the key intermediate contributing to this enhancement,model systems combining linoleic acid with A-X-ARP,Ala,and glyoxal(GO)were established,and the reaction products were analyzed.Ala,regenerated through the decomposition A-X-ARP,was identified as a crucial factor driving the production of enals and 1-octen-3-ol.Further thermal reaction models of linoleic acid with amino acids featuring diverse side chains revealed the universal catalytic effect of amino acids on enals and 1-octen-3-ol formation.Moreover,the amino group within amino acids was determined to be the key functional group responsible for this catalytic activity.Notably,the presence of amino acid was observed to reduce the oxygen dependence of linoleic acid oxidation in producing 1-octen-3-ol and enals.As a result,the addition of A-X-ARP during the thermal treatment of AEH increased the yield of 1-octen-3-ol,a compound with a typical mushroom-like note,from 19.3±3.7(OAV=19)to 71.4±9.8μg/L(OAV=71).These findings provided new insights for the development of mushroom-flavored seasonings.
基金supported by the National Key R&D Program of China (2017YFA0204704)the National Natural Science Foundation of China (21602105)+2 种基金the General Program of Chongqing Natural Science(cstc2020jcyj-msxmX0712)Ningbo Natural Science Foundation (202003N4063)the Natural Science Foundation of Jiangsu Province (BK20221309)
文摘Axially chiral molecules have been widely used in inorganic,material and medicinal chemistry.Compared with well-established N-heterocyclic carbene(NHC)-catalyzed asymmetric construction of centrally chiral molecules,NHC-catalyzed atroposelective synthesis of axially chiral molecules remains largely underdeveloped.Notably,alkynyl acyl azolium intermediates were commonly used in constructing a heteroaryl ring to furnish axially enantioenriched heteroaryl-aryls.The inherent character of the intermediates often led to react with sterically hindered substrates difficultly.Herein,we have successfully disclosed the atroposelective synthesis of axially chiral heteroaryl-aryls from sterically hindered enols through the use of chiral NHCs as catalysts for highly enantioselective Coates-Claisen rearrangements via catalytically generatedα,β-unsaturated acyl azoliums.This approach will enable the concise synthesis of valuable tetra-ortho-substituted 2-pyrones in one step with good yield and chirality control.
文摘Lacebark pine （Pinus bungeana）, an evergreen conifer species native to China, is noted for its graceful profile. It has a height up to 30 m. Bark on young trees smooth, dull grey, scaling off in small patches like a plane tree, changing to chalky-white on old trunks, by which the species can be recognized from a long distance.
基金Financial support from National Natural Science Foundation of China(Grant No.22201187)the starting grant from Capital Medical University(Grant No.3100-12400123)。
文摘With the hypothesis of simple units integration to create new reactivities,a strategy for the synthesis of polyfunctionalized 5-alkenyl-3-carbonylfurans fromγ-hydroxyl enal and 1,3-dicarbonyl compounds is established,featuring readily available starting materials,high efficiency,good functional groups compatibility,green chemistry with high atom economy and only water release,etc.,to provide a series of polyfunctionalized 5-alkenyl-3-carbonylfurans,which could be applied to the late-stage functionalization of naturally occurring compounds and bioactive molecules,as well as the transformation to pyrroles and polycyclic aromatic hydrocarbon via electrocyclic reaction.Theγ-hydroxyl has played an important role in the unexpected process of ring opening isomerization of 2H-pyran to furanones,as confirmed by detailed mechanistic studies.
基金the financial support from the National Science Foun-dation (CHE-1057569,W. W.)the China 111 Project (B07023,J. L. and W. W.)+1 种基金the National Natural Science Foundation of China (20972051,X. Y.-H.)the Science and Technology Commission of Shanghai Mu-nicipality (08430703900 & 08431901800,X. Y.-H.)
文摘A mild and highly efficient amine-catalyzed, IBX-mediated oxidation of aldehydes to （E） selective a, β-unsamrated aldehydes has been achieved in good yields. The process features a new oxidation of enamines to iminium ions in a catalytic fashion.
