The Smiles rearrangement is an exceptionally versatile method in organic synthesis,providing a broad canvas for designing cascade reactions that construct new Csp^(2)-Y(Y=C,O,N,S,CO,etc.)bonds.Among the various types ...The Smiles rearrangement is an exceptionally versatile method in organic synthesis,providing a broad canvas for designing cascade reactions that construct new Csp^(2)-Y(Y=C,O,N,S,CO,etc.)bonds.Among the various types of Smiles rearrangement,the radical-type variant has emerged as a more powerful,mild,efficient,and modern synthetic technique compared to its traditional ionic counterpart.This approach excels in generating new(hetero)aromatic migration products,enabling significant advancements in recent years.This tutorial review focuses on the recent progress,since 2016,in the development and application of radical Smiles rearrangement in organic chemistry.Special attention is paid to novel transformations achieved through photochemical,electrochemical,and transition metal catalysis methods.展开更多
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives.However,both the mechanistic activation mode and the...The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives.However,both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited.We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes,employing arylsulfonyl acetate as the bifunctional reagent.This approach involves a radical addition/Smiles rearrangement cascade process,offering a robust alternative for the synthesis of valuableγ,γ-diaryl andγ-aryl esters.A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions,facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity.Noteworthy features of this method include mild reaction conditions,organophotocatalysis,high atom-and step-economy,excellent functional group compatibility and great structural diversity.展开更多
In the negative ion mode of electrospray ionization tandem mass spectrometry （ES1-MS/MS） of four sulfonyl- urea herbicides, Smiles rearrangements were observed in rimsulfuron and nicosulfuron. In the case of rimsulf...In the negative ion mode of electrospray ionization tandem mass spectrometry （ES1-MS/MS） of four sulfonyl- urea herbicides, Smiles rearrangements were observed in rimsulfuron and nicosulfuron. In the case of rimsulfuron, two competitive gas-phase Smiles rearrangements initiated by nitrogen anion and oxygen anion respectively were witnessed. The ion-neutral complex was proposed as the reactive intermediate in the course of this unimoleeular dissociation reaction of the oxygen attack Smiles rearrangement route. The density functional theory （DFT） was carried out to elucidate the mechanism as well as to show the possible transition states and the intermediates.展开更多
A large-scale view of the magnetospheric cusp is expected to be obtained by the Soft X-ray Imager(SXI)onboard the Solar wind Magnetosphere Ionosphere Link Explorer(SMILE).However,it is challenging to trace the three-d...A large-scale view of the magnetospheric cusp is expected to be obtained by the Soft X-ray Imager(SXI)onboard the Solar wind Magnetosphere Ionosphere Link Explorer(SMILE).However,it is challenging to trace the three-dimensional cusp boundary from a two-dimensional X-ray image because the detected X-ray signals will be integrated along the line of sight.In this work,a global magnetohydrodynamic code was used to simulate the X-ray images and photon count images,assuming an interplanetary magnetic field with a pure Bz component.The assumption of an elliptic cusp boundary at a given altitude was used to trace the equatorward and poleward boundaries of the cusp from a simulated X-ray image.The average discrepancy was less than 0.1 RE.To reduce the influence of instrument effects and cosmic X-ray backgrounds,image denoising was considered before applying the method above to SXI photon count images.The cusp boundaries were reasonably reconstructed from the noisy X-ray image.展开更多
基金Financial support from the Fundamental Research Funds for Gannan Medical University(No.QD202429)National Natural Science Foundation of China(No.22171206)+2 种基金Natural Science Foundation of Zhejiang Province(No.LZ23B020001)Zhejiang Provincial Ten Thousand Talent Program(No.2023R5244)Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(No.2020ZD04)is gratefully acknowledged.
文摘The Smiles rearrangement is an exceptionally versatile method in organic synthesis,providing a broad canvas for designing cascade reactions that construct new Csp^(2)-Y(Y=C,O,N,S,CO,etc.)bonds.Among the various types of Smiles rearrangement,the radical-type variant has emerged as a more powerful,mild,efficient,and modern synthetic technique compared to its traditional ionic counterpart.This approach excels in generating new(hetero)aromatic migration products,enabling significant advancements in recent years.This tutorial review focuses on the recent progress,since 2016,in the development and application of radical Smiles rearrangement in organic chemistry.Special attention is paid to novel transformations achieved through photochemical,electrochemical,and transition metal catalysis methods.
基金the National Natural Science Foundation of China(No.21901199)National Training Program of Innovation and Entrepreneurship for Undergraduates(No.S202310698011)Xi’an Jiaotong University(No.7121192002)for financial support.
文摘The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives.However,both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited.We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes,employing arylsulfonyl acetate as the bifunctional reagent.This approach involves a radical addition/Smiles rearrangement cascade process,offering a robust alternative for the synthesis of valuableγ,γ-diaryl andγ-aryl esters.A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions,facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity.Noteworthy features of this method include mild reaction conditions,organophotocatalysis,high atom-and step-economy,excellent functional group compatibility and great structural diversity.
基金The authors gratefully acknowledge financial sup-port form the National Natural Science Foundation of China （Nos. 21025207 and 20975092）.
文摘In the negative ion mode of electrospray ionization tandem mass spectrometry （ES1-MS/MS） of four sulfonyl- urea herbicides, Smiles rearrangements were observed in rimsulfuron and nicosulfuron. In the case of rimsulfuron, two competitive gas-phase Smiles rearrangements initiated by nitrogen anion and oxygen anion respectively were witnessed. The ion-neutral complex was proposed as the reactive intermediate in the course of this unimoleeular dissociation reaction of the oxygen attack Smiles rearrangement route. The density functional theory （DFT） was carried out to elucidate the mechanism as well as to show the possible transition states and the intermediates.
基金funded by the National Natural Science Foundation of China(NNSFC)under Grant Numbers 42322408,42188101,and 42441809Additional support was provided by the Climbing Program of the National Space Science Center(NSSC,Grant No.E4PD3005)as well as the Specialized Research Fund for State Key Laboratories of China.
文摘A large-scale view of the magnetospheric cusp is expected to be obtained by the Soft X-ray Imager(SXI)onboard the Solar wind Magnetosphere Ionosphere Link Explorer(SMILE).However,it is challenging to trace the three-dimensional cusp boundary from a two-dimensional X-ray image because the detected X-ray signals will be integrated along the line of sight.In this work,a global magnetohydrodynamic code was used to simulate the X-ray images and photon count images,assuming an interplanetary magnetic field with a pure Bz component.The assumption of an elliptic cusp boundary at a given altitude was used to trace the equatorward and poleward boundaries of the cusp from a simulated X-ray image.The average discrepancy was less than 0.1 RE.To reduce the influence of instrument effects and cosmic X-ray backgrounds,image denoising was considered before applying the method above to SXI photon count images.The cusp boundaries were reasonably reconstructed from the noisy X-ray image.
