Herein, we reported an efficient and straightforward method to realize desaturated β-C(sp^(3))-H sulfonylation andphosphonylation of cyclic amines driven by electrochemistry using catalytic amounts of CP_(2)Fe as the...Herein, we reported an efficient and straightforward method to realize desaturated β-C(sp^(3))-H sulfonylation andphosphonylation of cyclic amines driven by electrochemistry using catalytic amounts of CP_(2)Fe as the redoxmediator. This protocol which had good functional group compatibility, provided the desired enaminyl sulfoneand enaminyl phosphine oxide products with high chemo- and regio-selectivity under mild conditions. Severalmechanistic studies have suggested that cyclic amines underwent multiple single-electron oxidation and deprotonation processes, followed by a capture step involving either a sulfonyl radical or a phosphonyl radical, ultimately leading to the desired products.展开更多
Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally ri...Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally rigid tridentate ketimine P,N,N ligand, a series of optically active phosphonylated 2,3‐dihydrofurans were prepared in high yield and up to 92%ee.展开更多
Antigen 12, containing a phosphonyl peptide hapten with free C-terminal carboxylic group, was synthesized by 11 reaction steps. The design of the hapten was based on the transition state of peptide hydrolysis catalyze...Antigen 12, containing a phosphonyl peptide hapten with free C-terminal carboxylic group, was synthesized by 11 reaction steps. The design of the hapten was based on the transition state of peptide hydrolysis catalyzed by carboxypeptidase A.展开更多
The Arbuzov reaction(also known as the Michaelis–Arbuzov reaction)is one of the most fundamental transformations in organic chemistry and has been extensively used for the synthesis of organophosphorus compounds for ...The Arbuzov reaction(also known as the Michaelis–Arbuzov reaction)is one of the most fundamental transformations in organic chemistry and has been extensively used for the synthesis of organophosphorus compounds for over a century.However,the reaction generally requires an elevated temperature and is applicable mainly to primary alkyl halides with poor functional group tolerance.We report herein a radical alternative to the conventional nucleophilic substitution reaction.Thus,new radical phosphonylation reagents,9-fluorenyl o-phenylene phosphite and benzhydryl o-phenylene phosphite,have been developed for this purpose.The photoredox-catalyzed reaction of a wide range of alkyl bromides or iodides with 9-fluorenyl(or benzhydryl)o-phenylene phosphite followed by workup with methanol(or ethanol)provides the corresponding dimethyl(or diethyl)alkylphosphonates in satisfactory yields at room temperature under mild conditions.The method is applicable to primary,secondary,and even tertiary alkyl iodides and bromides and exhibits an excellent functional group tolerance,thereby enabling the late-stage modification of complex molecules and rapid synthesis of phosphonate-containing natural products and drug molecules.A mechanism involving the formation and subsequentβ-scission of phosphoranyl radicals is proposed.展开更多
This paper presents nine novel pyrethroids containing phosphorous and five new phos- phorous ylids.A new synthetic route of β-substituted vinyl(thio)phosphonate having E configura- tion have been developed.The compou...This paper presents nine novel pyrethroids containing phosphorous and five new phos- phorous ylids.A new synthetic route of β-substituted vinyl(thio)phosphonate having E configura- tion have been developed.The compound li exhibited moderate insecticidal activities against Culex mosquitoes and Army worm.展开更多
基金National Natural Science Foundation of China(Nos.22178315,22378363,22078298 and 21978271)the Natural Science Foundation of Zhejiang Province of China(No.LY21B020007)+1 种基金China Postdoctoral Science Foundation(No.2022M712824)Key Research and Development Program of Zhejiang Province(No.2022C03169)for financial support.
文摘Herein, we reported an efficient and straightforward method to realize desaturated β-C(sp^(3))-H sulfonylation andphosphonylation of cyclic amines driven by electrochemistry using catalytic amounts of CP_(2)Fe as the redoxmediator. This protocol which had good functional group compatibility, provided the desired enaminyl sulfoneand enaminyl phosphine oxide products with high chemo- and regio-selectivity under mild conditions. Severalmechanistic studies have suggested that cyclic amines underwent multiple single-electron oxidation and deprotonation processes, followed by a capture step involving either a sulfonyl radical or a phosphonyl radical, ultimately leading to the desired products.
基金supported by the National Natural Science Foundation of China (21403022,21572226)the Natural Science Foundation of Liaoning Province of China (2015020194)~~
文摘Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally rigid tridentate ketimine P,N,N ligand, a series of optically active phosphonylated 2,3‐dihydrofurans were prepared in high yield and up to 92%ee.
文摘Antigen 12, containing a phosphonyl peptide hapten with free C-terminal carboxylic group, was synthesized by 11 reaction steps. The design of the hapten was based on the transition state of peptide hydrolysis catalyzed by carboxypeptidase A.
基金the National Natural Science Foundation of China(grant nos.22193012,22193014,22122104,21933004,and 21971253)the Chinese Academy of Sciences(grant no.ZDBS-LY-SLH026)+1 种基金the Youth Promotion Association(grant no.2020257)the Chinese Academy of Sciences,and the Science and Technology Commission of Shanghai Municipality(grant nos.21ZR1476700 and 21YF1456300).
文摘The Arbuzov reaction(also known as the Michaelis–Arbuzov reaction)is one of the most fundamental transformations in organic chemistry and has been extensively used for the synthesis of organophosphorus compounds for over a century.However,the reaction generally requires an elevated temperature and is applicable mainly to primary alkyl halides with poor functional group tolerance.We report herein a radical alternative to the conventional nucleophilic substitution reaction.Thus,new radical phosphonylation reagents,9-fluorenyl o-phenylene phosphite and benzhydryl o-phenylene phosphite,have been developed for this purpose.The photoredox-catalyzed reaction of a wide range of alkyl bromides or iodides with 9-fluorenyl(or benzhydryl)o-phenylene phosphite followed by workup with methanol(or ethanol)provides the corresponding dimethyl(or diethyl)alkylphosphonates in satisfactory yields at room temperature under mild conditions.The method is applicable to primary,secondary,and even tertiary alkyl iodides and bromides and exhibits an excellent functional group tolerance,thereby enabling the late-stage modification of complex molecules and rapid synthesis of phosphonate-containing natural products and drug molecules.A mechanism involving the formation and subsequentβ-scission of phosphoranyl radicals is proposed.
文摘This paper presents nine novel pyrethroids containing phosphorous and five new phos- phorous ylids.A new synthetic route of β-substituted vinyl(thio)phosphonate having E configura- tion have been developed.The compound li exhibited moderate insecticidal activities against Culex mosquitoes and Army worm.
