The influence of metal cations on 13C-18O bonds in carbonates is still under debate. This paper used ab initio method to investigate this kind of influence of Mg2+, Fe2+ and Zn2+ cations on 13C-18O bonds in precipitat...The influence of metal cations on 13C-18O bonds in carbonates is still under debate. This paper used ab initio method to investigate this kind of influence of Mg2+, Fe2+ and Zn2+ cations on 13C-18O bonds in precipitated aragonite, calcite and dolomite. The polynomials of Δ47 and reduced partition function ratios (RPFRs) for 13/12C, 14/12C and 18/16O of these minerals were given within temperatures ranging from 260 to 1500 K. We found that these cations significantly decreased the Δ47 values at the level of 10-3 - 10-2 per mil, comparing with pure crystals;and that if the Δ47 values were used to reconstruct the temperatures Ts, the deviation of T was about 7.2°C for, for instance, zinc-enriched aragonite, as discussed in our paper. It was suggested that due to such influence, researchers would better use a proper thermometer according to the main impurity metal cations in carbonates. We also found that according to the probability theory, the theoretical value of the influence of phosphoric acid on Δ47 of CO2 degassed from different carbonates was zero.展开更多
The 13C-18O bonds in carbonates are potential single-phase geo-thermometers. However, their theoretical distributions (noted as Δ47s) in CO2 degassed from calcite and aragonite with phosphoric acid are unclear. Thus,...The 13C-18O bonds in carbonates are potential single-phase geo-thermometers. However, their theoretical distributions (noted as Δ47s) in CO2 degassed from calcite and aragonite with phosphoric acid are unclear. Thus, the isotope reactions of 13C-18O bonds on the growing surfaces of calcite (0001) and aragonite (001) planes were investigated using ab initio techniques. It was found that these reactions determined 13C-18O clumped isotope signatures in bulk calcite and aragonite minerals with novel Δ47 polynomials: and for temperatures ranging from 260 to 1500 K. These theoretical results were in good agreement with the experimental data. In addition, the influence of phosphoric acid on these polynomials was at the level of 0.01‰.展开更多
Chiral organosulfur compounds are not only widely distributed in bioactive natural products and pharmaceuticals,but also play a significant role in chiral ligands/catalysts.Throughout the history of synthetic organic ...Chiral organosulfur compounds are not only widely distributed in bioactive natural products and pharmaceuticals,but also play a significant role in chiral ligands/catalysts.Throughout the history of synthetic organic chemistry,chemists have been absorbed in the construction of centrally chiral organosulfur compounds.Nevertheless,there are relatively few reports on installing sulfur functional groups into axially chiral compounds.Atropisomerism is one of the fundamental phenomena in nature,which ubiquitously exists in natural products.After more than a century of development,atropisomers have been designed and extensively applied to pharmaceuticals,functional materials and chiral ligands/catalysts.Due to the importance of chiral sulfurcontaining atropisomers,there is an increasing demand for enantioselective synthesis of them.Recently,a diversity of approaches by C-S bond formations have been established for the construction of enantioenriched sulfur-containing atropisomers,however,there is no comprehensive review to summarize this great progress.In this mini-review,we summarize recent progress in catalytic asymmetric synthesis of sulfur-containing atropisomers by C-S bond formations,which includes sulfur nucleophilic reactions,sulfur electrophilic reactions and sulfur radical reactions.Furthermore,the reaction mechanisms are also discussed.We hope that this mini-review will enable more researchers to further explore this field.展开更多
Achieving highly regioselective synthesis in organic chemistry is challenging due to the uncontrollable orientation between reacting partners.External electric fields(EEFs)can influence the reactivity and selectivity ...Achieving highly regioselective synthesis in organic chemistry is challenging due to the uncontrollable orientation between reacting partners.External electric fields(EEFs)can influence the reactivity and selectivity of the substrate by causing directional adsorption.However,scalable and efficient techniques for using EEFs as“smart catalysts”have been lacking,hindering their application.In this study,we present a novel method for modifying the regioselectivity of quinoxaline-2(1H)-ones by functionalizing their C7-position using the electric double layer(EDL)theory.This approach led to moderate to good yields of the corresponding C7-thiocyanation products.DFT calculations and control experiments demonstrated that EEFs could reverse the regioselectivity of quinoxaline-2(1H)-ones,allowing the C7-thiocyanation to proceed via a radical reaction mechanism.Additionally,the resulting 7-thiocyano-1-methylquinoxaline-2(1H)-ones exhibited promising AIE properties.Our work showcases a promising strategy for achieving highly regioselective functionalization by aligning the electric field with the desired reaction/bond axis.展开更多
An efficient and practical synthetic protocol to synthesize nonsymmetrical aryl thioethers by nucleophilic aromatic substitution(S_NAr)reaction of nitroarenes by thiols with potassium phosphate as the catalyst is desc...An efficient and practical synthetic protocol to synthesize nonsymmetrical aryl thioethers by nucleophilic aromatic substitution(S_NAr)reaction of nitroarenes by thiols with potassium phosphate as the catalyst is described.Various moderate to strong electron-withdrawing functional groups are tolerated by the system to provide thioethers in a good to excellent yields.We also showed that the present method allows access to 3 drug examples in a short reaction time.Finally,mechanistic studies suggest that the reaction may form the classic Meisenheimer complex through a two-step additionelimination mechanism.展开更多
An efficient approach to sulfur-bridged imidazopyridines has been developed under metal-free conditions using inexpensive sulfur powder as the sulfur source.Most appealingly,the reaction can proceed smoothly without a...An efficient approach to sulfur-bridged imidazopyridines has been developed under metal-free conditions using inexpensive sulfur powder as the sulfur source.Most appealingly,the reaction can proceed smoothly without addition of any additives,ultimately decreasing the production of chemical waste.The inexpensive and green method should provide a useful strategy for constructing a library of novel and biological interesting heteroaromatic sulfides.展开更多
Potassium tert-butoxide has been found to be a highly efficient catalyst for one-pot,three-component reaction of aryl aldehydes, acetophenones,and thiols via Claisen-Schmidt/Michael addition reactions for the synthesi...Potassium tert-butoxide has been found to be a highly efficient catalyst for one-pot,three-component reaction of aryl aldehydes, acetophenones,and thiols via Claisen-Schmidt/Michael addition reactions for the synthesis of thia-Michael adducts in high yields. The reactions are best carried out in tert-butyl alcohol at room temperature.展开更多
Herein,we report a borane-promoted reductive deoxygenation coupling reaction to synthesize sulfides.This reaction features excellent functional group compatibility,high efficiency,broad substrate scope,and application...Herein,we report a borane-promoted reductive deoxygenation coupling reaction to synthesize sulfides.This reaction features excellent functional group compatibility,high efficiency,broad substrate scope,and application in late-stage functionalization of biomolecules.Preliminary mechanistic studies suggest diaryl sulfides are the intermediates of this reaction.Moreover,the real active aryl sulfide anions may be generated in situ with the aid of B2pin2 and react with alkyl tosylates through a concerted SN2 pathway.展开更多
Methods for the carbon-sulfur bond formation under catalyst-free,aqueous conditions are extremely useful in organic synthesis and chemical biology.Our laboratory has developed methodologies to construct carbon-thiol b...Methods for the carbon-sulfur bond formation under catalyst-free,aqueous conditions are extremely useful in organic synthesis and chemical biology.Our laboratory has developed methodologies to construct carbon-thiol bonds,carbon-sulfinic acid bonds,and carbon-disulfide bonds and such methodologies have been widely adopted by other research groups over multidisciplinary fields.In this article,our work on C-S bond formation in an aqueous solvent and its corresponding applications is summarized.展开更多
The development of green and convenient methods for C–S bond formation has received significant attention because C–S bond widely occurs in many important pharmaceutical and biological compounds.Recently, visible-li...The development of green and convenient methods for C–S bond formation has received significant attention because C–S bond widely occurs in many important pharmaceutical and biological compounds.Recently, visible-light photoredox catalysis has been established as an efficient and general tool for the construction of C–C and C-heteroatom bonds. In this review, we have focused on the research on recent advances in C–S bond formation via visible-light photoredox catalysis, and the growing opportunities they present to the construction of complex chemical scaffolds for applications encompassing bioactive molecules synthesis, synthetic methodology development, and sulfur-containing drugs. We hope that this review will provide chemists with a synthetic tool that will open the door to further development of organsulfur chemistry.展开更多
A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described.The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond.Under ac...A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described.The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond.Under acidic conditions,sulfonium ylides serve as alkyl cation precursors which facilitate the alkylations.While under alkaline conditions,cleavage of non-ylidic S-aryl bond produces O-arylated compounds efficiently.The robustness of the protocols were established by the excellent compatibility of wide variety of substrates including carbohydrates.展开更多
An efficient and eco-friendly protocol for the construction of naphtho[2,1-d]thiazol-2-amines through visible-light photoredox-catalyzed C(sp2)–H/S–H cross-dehydrogenative coupling reactions between 2-isothiocyanato...An efficient and eco-friendly protocol for the construction of naphtho[2,1-d]thiazol-2-amines through visible-light photoredox-catalyzed C(sp2)–H/S–H cross-dehydrogenative coupling reactions between 2-isothiocyanatonaphthalenes and amines was established.In this reaction,the new C–N and C–S bonds are formed simultaneously in a single step.This new method provides a straightforward approach for constructing valuable sulfur-containing compounds.展开更多
High abundant sulfur-containing steroids were identified and detected in saturate hydrocarbon fractions of heavy oil with a high sulfur content in the Jinxian Sag,Bohai Bay Basin,North China.These sulfur-containing st...High abundant sulfur-containing steroids were identified and detected in saturate hydrocarbon fractions of heavy oil with a high sulfur content in the Jinxian Sag,Bohai Bay Basin,North China.These sulfur-containing steroids were structurally merged into the D-ring of steroid nucleus with thiophene ring and/or combined into the C-22 in the side-chain.Based on the previous reports of sulfur-containing steroids with methylthio-steroids and intra-molecular form,four formation mechanisms of sulfur-containing steroids and diagenetic pathway of steroids under S-rich conditions were proposed in this paper according to the double bond positions in the sterene compounds.Hydrogenation and sulfurization both occurred in the diagenetic processes of olefinic bond in the side-chain of steroids:abiogenic chemical hydrogenation of H2S and HS-leads to the formation of regular steranes;a successful sulfurization process leads to the formation of the side-chain sulfur-containing steroids whereas unsuccessful cyclization and/or sulfurization result in the generation of short-chain steranes.This kind of mechanism of hydrogenation/sulfurization of side-chain olefinic bond provides a potential genesis clue for the occurrence of high abundance of short-chain steranes(higher than the common regular steroids,phytane and n-alkanes)in S-rich heavy oils and source rocks in the Jinxian Sag,Bohai Bay Basin,North China.展开更多
文摘The influence of metal cations on 13C-18O bonds in carbonates is still under debate. This paper used ab initio method to investigate this kind of influence of Mg2+, Fe2+ and Zn2+ cations on 13C-18O bonds in precipitated aragonite, calcite and dolomite. The polynomials of Δ47 and reduced partition function ratios (RPFRs) for 13/12C, 14/12C and 18/16O of these minerals were given within temperatures ranging from 260 to 1500 K. We found that these cations significantly decreased the Δ47 values at the level of 10-3 - 10-2 per mil, comparing with pure crystals;and that if the Δ47 values were used to reconstruct the temperatures Ts, the deviation of T was about 7.2°C for, for instance, zinc-enriched aragonite, as discussed in our paper. It was suggested that due to such influence, researchers would better use a proper thermometer according to the main impurity metal cations in carbonates. We also found that according to the probability theory, the theoretical value of the influence of phosphoric acid on Δ47 of CO2 degassed from different carbonates was zero.
文摘The 13C-18O bonds in carbonates are potential single-phase geo-thermometers. However, their theoretical distributions (noted as Δ47s) in CO2 degassed from calcite and aragonite with phosphoric acid are unclear. Thus, the isotope reactions of 13C-18O bonds on the growing surfaces of calcite (0001) and aragonite (001) planes were investigated using ab initio techniques. It was found that these reactions determined 13C-18O clumped isotope signatures in bulk calcite and aragonite minerals with novel Δ47 polynomials: and for temperatures ranging from 260 to 1500 K. These theoretical results were in good agreement with the experimental data. In addition, the influence of phosphoric acid on these polynomials was at the level of 0.01‰.
基金supported by the National Natural Science Foundation of China (22071149,21871178)the Natural Science Foundation of Shanghai (23ZR1428200)the Program for Professor of Special Appointment (Eastern Scholar)at Shanghai Institutions of Higher Learning。
文摘Chiral organosulfur compounds are not only widely distributed in bioactive natural products and pharmaceuticals,but also play a significant role in chiral ligands/catalysts.Throughout the history of synthetic organic chemistry,chemists have been absorbed in the construction of centrally chiral organosulfur compounds.Nevertheless,there are relatively few reports on installing sulfur functional groups into axially chiral compounds.Atropisomerism is one of the fundamental phenomena in nature,which ubiquitously exists in natural products.After more than a century of development,atropisomers have been designed and extensively applied to pharmaceuticals,functional materials and chiral ligands/catalysts.Due to the importance of chiral sulfurcontaining atropisomers,there is an increasing demand for enantioselective synthesis of them.Recently,a diversity of approaches by C-S bond formations have been established for the construction of enantioenriched sulfur-containing atropisomers,however,there is no comprehensive review to summarize this great progress.In this mini-review,we summarize recent progress in catalytic asymmetric synthesis of sulfur-containing atropisomers by C-S bond formations,which includes sulfur nucleophilic reactions,sulfur electrophilic reactions and sulfur radical reactions.Furthermore,the reaction mechanisms are also discussed.We hope that this mini-review will enable more researchers to further explore this field.
基金supported by the National Natural Science Foundation of China(21172200,21302172)the Basic Research Training Project of Zhengzhou University(JC2020053021)supported by the National Research Foundation of Korea(CRI Project No.2018R1A3B1052702 for Jong Seung Kim)。
文摘Achieving highly regioselective synthesis in organic chemistry is challenging due to the uncontrollable orientation between reacting partners.External electric fields(EEFs)can influence the reactivity and selectivity of the substrate by causing directional adsorption.However,scalable and efficient techniques for using EEFs as“smart catalysts”have been lacking,hindering their application.In this study,we present a novel method for modifying the regioselectivity of quinoxaline-2(1H)-ones by functionalizing their C7-position using the electric double layer(EDL)theory.This approach led to moderate to good yields of the corresponding C7-thiocyanation products.DFT calculations and control experiments demonstrated that EEFs could reverse the regioselectivity of quinoxaline-2(1H)-ones,allowing the C7-thiocyanation to proceed via a radical reaction mechanism.Additionally,the resulting 7-thiocyano-1-methylquinoxaline-2(1H)-ones exhibited promising AIE properties.Our work showcases a promising strategy for achieving highly regioselective functionalization by aligning the electric field with the desired reaction/bond axis.
基金financial support by the National Natural Science Foundation of China (No.U1532135)
文摘An efficient and practical synthetic protocol to synthesize nonsymmetrical aryl thioethers by nucleophilic aromatic substitution(S_NAr)reaction of nitroarenes by thiols with potassium phosphate as the catalyst is described.Various moderate to strong electron-withdrawing functional groups are tolerated by the system to provide thioethers in a good to excellent yields.We also showed that the present method allows access to 3 drug examples in a short reaction time.Finally,mechanistic studies suggest that the reaction may form the classic Meisenheimer complex through a two-step additionelimination mechanism.
基金This work was supported by the National Natural Science Foundation of China(No.21302110)the Natural Science Foundation of Shandong Province(No.ZR2016JL012)the Scientific Research Foundation of Qingdao University of Science and Technology.
文摘An efficient approach to sulfur-bridged imidazopyridines has been developed under metal-free conditions using inexpensive sulfur powder as the sulfur source.Most appealingly,the reaction can proceed smoothly without addition of any additives,ultimately decreasing the production of chemical waste.The inexpensive and green method should provide a useful strategy for constructing a library of novel and biological interesting heteroaromatic sulfides.
文摘Potassium tert-butoxide has been found to be a highly efficient catalyst for one-pot,three-component reaction of aryl aldehydes, acetophenones,and thiols via Claisen-Schmidt/Michael addition reactions for the synthesis of thia-Michael adducts in high yields. The reactions are best carried out in tert-butyl alcohol at room temperature.
基金support from Natural Science Foundation of Sichuan(No.2021YJ0413)Sichuan Key Laboratory of Medical Imaging(North Sichuan Medical College,No.SKLMI201901)+2 种基金Strategic Cooperation of Science and Technology between Nanchong City and North Sichuan Medical College(Nos.19SXHZ0441,19SXHZ0227)Chongqing Postdoctoral Science Foundation(No.cstc2020jcyj-bshX0052)China Postdoctoral Science Foundation(No.2020M673121).
文摘Herein,we report a borane-promoted reductive deoxygenation coupling reaction to synthesize sulfides.This reaction features excellent functional group compatibility,high efficiency,broad substrate scope,and application in late-stage functionalization of biomolecules.Preliminary mechanistic studies suggest diaryl sulfides are the intermediates of this reaction.Moreover,the real active aryl sulfide anions may be generated in situ with the aid of B2pin2 and react with alkyl tosylates through a concerted SN2 pathway.
基金We gratefully acknowledge the financial support from the Distinguished University Professor grant(Nanyang Technological University),AcRF Tier 1 grants from the Ministry of Education of Singapore(Nos.RG11/20 and RT14/20)the Agency for Science,Technology and Research(A*STAR)for its MTC Individual Research Grant(No.M21K2c0114).
文摘Methods for the carbon-sulfur bond formation under catalyst-free,aqueous conditions are extremely useful in organic synthesis and chemical biology.Our laboratory has developed methodologies to construct carbon-thiol bonds,carbon-sulfinic acid bonds,and carbon-disulfide bonds and such methodologies have been widely adopted by other research groups over multidisciplinary fields.In this article,our work on C-S bond formation in an aqueous solvent and its corresponding applications is summarized.
基金supported by the Natural Science Foundation of Shandong Province (No. ZR2016JL012)Hunan Provincial Natural Science Foundation of China (No. 2019JJ20008)the Scientific Research Foundation of Qingdao University of Science and Technology (No. 1203043003457)。
文摘The development of green and convenient methods for C–S bond formation has received significant attention because C–S bond widely occurs in many important pharmaceutical and biological compounds.Recently, visible-light photoredox catalysis has been established as an efficient and general tool for the construction of C–C and C-heteroatom bonds. In this review, we have focused on the research on recent advances in C–S bond formation via visible-light photoredox catalysis, and the growing opportunities they present to the construction of complex chemical scaffolds for applications encompassing bioactive molecules synthesis, synthetic methodology development, and sulfur-containing drugs. We hope that this review will provide chemists with a synthetic tool that will open the door to further development of organsulfur chemistry.
基金Financial support from National Natural Science Foundation of China(Nos.21877043,21702068,21772050,22025102)the Fundamental Research Funds for the Central Universities,HUST(Nos.2019kfyXKJC080,2019JYCXJJ046)Huazhong University of Science and Technology are greatly appreciated。
文摘A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described.The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond.Under acidic conditions,sulfonium ylides serve as alkyl cation precursors which facilitate the alkylations.While under alkaline conditions,cleavage of non-ylidic S-aryl bond produces O-arylated compounds efficiently.The robustness of the protocols were established by the excellent compatibility of wide variety of substrates including carbohydrates.
基金This work was supported by the National Natural Science Foundation of China(21302110,21702119)the Natural Science Foundation of Shandong Province(ZR2016JL012,ZR2017QB001)+1 种基金the Scientific Research Foundation of Qingdao University of Science and Technology,the Natural Science Foundation of Liaoning Province(20180550882)the Program for Creative Talents in University of Liaoning Province.
文摘An efficient and eco-friendly protocol for the construction of naphtho[2,1-d]thiazol-2-amines through visible-light photoredox-catalyzed C(sp2)–H/S–H cross-dehydrogenative coupling reactions between 2-isothiocyanatonaphthalenes and amines was established.In this reaction,the new C–N and C–S bonds are formed simultaneously in a single step.This new method provides a straightforward approach for constructing valuable sulfur-containing compounds.
基金supported by National Basic Research Program of China(Grant No.2012CB701404)Major National Science and Technology Project(Grant No.2011ZX05008-002-33)+2 种基金National Natural Science Foundation of China(Grant Nos.40873048,41173053)Gas Hydrate Survey in South Sea of China(Grant No.GZH2011003-05-04-01)This isa contribution to No.IS-1689 from Guangzhou Institute of Geochemistry,Chinese Academy of Sciences
文摘High abundant sulfur-containing steroids were identified and detected in saturate hydrocarbon fractions of heavy oil with a high sulfur content in the Jinxian Sag,Bohai Bay Basin,North China.These sulfur-containing steroids were structurally merged into the D-ring of steroid nucleus with thiophene ring and/or combined into the C-22 in the side-chain.Based on the previous reports of sulfur-containing steroids with methylthio-steroids and intra-molecular form,four formation mechanisms of sulfur-containing steroids and diagenetic pathway of steroids under S-rich conditions were proposed in this paper according to the double bond positions in the sterene compounds.Hydrogenation and sulfurization both occurred in the diagenetic processes of olefinic bond in the side-chain of steroids:abiogenic chemical hydrogenation of H2S and HS-leads to the formation of regular steranes;a successful sulfurization process leads to the formation of the side-chain sulfur-containing steroids whereas unsuccessful cyclization and/or sulfurization result in the generation of short-chain steranes.This kind of mechanism of hydrogenation/sulfurization of side-chain olefinic bond provides a potential genesis clue for the occurrence of high abundance of short-chain steranes(higher than the common regular steroids,phytane and n-alkanes)in S-rich heavy oils and source rocks in the Jinxian Sag,Bohai Bay Basin,North China.