A general method was described to synthesize a highly hydrophobic cyclic peptide,cyclo[LWLWLWLWLQ]where underlines indicate D-configuration of the amino acid,by a two-step solid-phase/solution synthesis strategy.The l...A general method was described to synthesize a highly hydrophobic cyclic peptide,cyclo[LWLWLWLWLQ]where underlines indicate D-configuration of the amino acid,by a two-step solid-phase/solution synthesis strategy.The linear decapeptide was assembled by standard Boc chemistry on solid-phase and subsequently cyclized in solution with high efficiency and reproducibility. In subsequent purification by semi-preparative HPLC,50%(v/v) DMF/H_2O was employed as the solvent to overcome the difficulty of solubilization...展开更多
A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yi...A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.展开更多
Compared to the widely used carbon-centered radicals,N-radicals have been relatively unexplored owing to the lack of practical and convenient production methods.Over the past few years,benefitting from the resurgence ...Compared to the widely used carbon-centered radicals,N-radicals have been relatively unexplored owing to the lack of practical and convenient production methods.Over the past few years,benefitting from the resurgence of reliable and controllable radical chemistry,N-radicals have been produced via thermal decomposition,oxidants,metal salts,or electrocatalysis.Therefore,numerous N-radical enabled cyclization of 1,n-enynes methods have been developed,providing a versatile and concise synthetic platform for the preparation of complex cyclic systems and natural products containing elaborate ring frameworks.In this review,we will summarize recent advances in the promising field of radical chemistry focusing on the production methods of N-radicals and their cyclization patterns,associated mechanisms,unmet challenges,and future opportunities.展开更多
1-[1-(Benzyloxy)-3-methylnaphthalen-4-yloxy]propan-2-one (la) took place a cyclization, debenzylation and oxidation to form 9-substitued benzo[de]chromene-7,8-dione (2a) and 5-benzyl-9-substitued benzo[de]chrome...1-[1-(Benzyloxy)-3-methylnaphthalen-4-yloxy]propan-2-one (la) took place a cyclization, debenzylation and oxidation to form 9-substitued benzo[de]chromene-7,8-dione (2a) and 5-benzyl-9-substitued benzo[de]chromene-7,8-dione (3a). The mechanisms for these reactions were discussed.展开更多
Stereoselective functionalization at C-2 and C-3 of the gibberellin skeleton was achieved via an intramolecular free radical cyclization approach using a tethered C-19 halomethyl ester as the radical precursor.
The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative...The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative cyclization of a variety of alkynic hydrazones with carbon dioxide to produce the corresponding 1,3,4-oxadiazin-2-ones under mild reaction conditions. In this reaction, silver(I) salts play a π-Lewis acid role for the highly efficient activation of the alkyne moiety in the hydrazone substrates. Single-crystal X-ray analysis and NOE experiments confirm that the newly formed oxadiazinone products exhibit Z configuration. Based on control experiments and NMR studies, a mechanism including the formation of a reactive carbazate intermediate, electrophilic cyclization, and subsequent protonation is proposed. This study offers an efficient and atom- economical method for the synthesis of biologically important 1,3,4-oxadiazin-2-ones.展开更多
new method to synthesize heterocycle-fused troponoid compounds by oxidizing azocoupling products of 3-isopropenyltropolone and 3-cinnamoyltropolone with bromine in the presence of pyridine was reported for the first t...new method to synthesize heterocycle-fused troponoid compounds by oxidizing azocoupling products of 3-isopropenyltropolone and 3-cinnamoyltropolone with bromine in the presence of pyridine was reported for the first time. Reaction of azo-couping products of 3-isopropenyl tropolone 1a similar to f and 3-cinnamoyltropolone 3a similar to d with excess bromine afforded heterocycle-fused troponoid compounds 2a similar to f, 4a similar to d, respectively.展开更多
A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excel...A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excellent yields.展开更多
Substituted 2-halomethyl-2,3-dihydrobenzofurans were synthesized in one pot and in mild yield from substituted o-allylphenols with diacetoxyiodobenzene in the presence of 12 or Br2 in dry CH2Cl2 under reflux.
The reaction of α-triazolyl-α, β-unsaturated ketones with phenyl hydrazine was studied. The result indicated that cyclization took place and new heterocyclic compounds of substituted 4,5-2H-pyrazoles were obtained,...The reaction of α-triazolyl-α, β-unsaturated ketones with phenyl hydrazine was studied. The result indicated that cyclization took place and new heterocyclic compounds of substituted 4,5-2H-pyrazoles were obtained, whose structures and conformation were characterized by 1H NMR, IR, MS, elemental analysis and X-ray diffraction.展开更多
A novel macrolactonization method was developed using a chiral β-lactam as the template. This novel method features that the macrocyclization is simultaneously achieved while a TBS protected hydroxy group is deprotec...A novel macrolactonization method was developed using a chiral β-lactam as the template. This novel method features that the macrocyclization is simultaneously achieved while a TBS protected hydroxy group is deprotected.展开更多
Intramolecular cyclization of A catalyzed by IDA in benzene or THF yields two γ-lactams through C-alkylation and one δ-and one 7-membered lactam by O-alkylation.
An effective approach for the construction of the decalin ring skeleton of labdane diterpenoids was developed based on a key biomimetic cationic polyene cyclization of an epoxy allylsilane precursor. The synthetic a...An effective approach for the construction of the decalin ring skeleton of labdane diterpenoids was developed based on a key biomimetic cationic polyene cyclization of an epoxy allylsilane precursor. The synthetic approach demonstrated here would be useful in the enantioselective and diastereoselective total synthesis of natural labdane diterpenoids in general.展开更多
The Lewis acid mediated polystyrene supported selenium cyclization of chalcones and oxidative cleavage of selenium resins flavonoids in good yields and purities have been reported. induced intramolecular gave the cor...The Lewis acid mediated polystyrene supported selenium cyclization of chalcones and oxidative cleavage of selenium resins flavonoids in good yields and purities have been reported. induced intramolecular gave the corresponding展开更多
Some new benzimidazoles and benzoxazoles have been prepared under mild condition by oxidative cyclization of arylaldehyde witho-phenylenediamine ando-aminophenol using potassium ferricyanide as oxidant
The cyclization reaction of D-aspartic acid was studied, the carboxyl groups of D-aspartic acid were protected by benzyl alcohol to give compound D-dibenzyl aspartate. Then (4R)-benzyl azetidine-2-one-4-carboxylate ...The cyclization reaction of D-aspartic acid was studied, the carboxyl groups of D-aspartic acid were protected by benzyl alcohol to give compound D-dibenzyl aspartate. Then (4R)-benzyl azetidine-2-one-4-carboxylate and meso-3,6-disubstituted piperazine-2,5-diones were synthesized via intramolecular cyclization and intermolecular cycfization of D-dibenzyl aspartate, respectively, and their structures were confirmed by ^1 H NMR and MS. Both cyclization reaction conditions were also investigated in detail.展开更多
A highly efficient and direct approach was developed to construct the structurally diverse spirooxindole skeleton,which is an important basic motif in natural products.Both the 3,30-pyrrolidonyl spirooxindoles and spi...A highly efficient and direct approach was developed to construct the structurally diverse spirooxindole skeleton,which is an important basic motif in natural products.Both the 3,30-pyrrolidonyl spirooxindoles and spiroindolin-2-one dlactones were 2smoothly obtained by the intramolecular Dieckmann cyclization of oxindoles in excellent yield under mild conditions.展开更多
The major products of carbonium cyclization of 1 are 2 and 3;2 is unstable and undergoes aerial oxidation to give 4.A similar product(6)from 5 is somehow stabilized by the extra ben- zoyloxy group(or OH)and can be sto...The major products of carbonium cyclization of 1 are 2 and 3;2 is unstable and undergoes aerial oxidation to give 4.A similar product(6)from 5 is somehow stabilized by the extra ben- zoyloxy group(or OH)and can be stored without deterioration.展开更多
基金supported by National Natural Science Foundation(No.30672546)Shanghai Municipal Committee of S & T(No.0652nm013)National Key Basic Research Program of China(No.2007CB935800)
文摘A general method was described to synthesize a highly hydrophobic cyclic peptide,cyclo[LWLWLWLWLQ]where underlines indicate D-configuration of the amino acid,by a two-step solid-phase/solution synthesis strategy.The linear decapeptide was assembled by standard Boc chemistry on solid-phase and subsequently cyclized in solution with high efficiency and reproducibility. In subsequent purification by semi-preparative HPLC,50%(v/v) DMF/H_2O was employed as the solvent to overcome the difficulty of solubilization...
文摘A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.
文摘Compared to the widely used carbon-centered radicals,N-radicals have been relatively unexplored owing to the lack of practical and convenient production methods.Over the past few years,benefitting from the resurgence of reliable and controllable radical chemistry,N-radicals have been produced via thermal decomposition,oxidants,metal salts,or electrocatalysis.Therefore,numerous N-radical enabled cyclization of 1,n-enynes methods have been developed,providing a versatile and concise synthetic platform for the preparation of complex cyclic systems and natural products containing elaborate ring frameworks.In this review,we will summarize recent advances in the promising field of radical chemistry focusing on the production methods of N-radicals and their cyclization patterns,associated mechanisms,unmet challenges,and future opportunities.
基金We are indebted to the National Natural Science Foundation of China (No.20272085,20472117)the Guangzhou City Science Foundation,the Guangdong Provincial Science Foundation(031594)the Scientific Research Foundation for the Returned 0verseas Chinese Scholars,and the HongKong Polytechnic University Area of Strategic Development Fund for financial support of this study.
文摘1-[1-(Benzyloxy)-3-methylnaphthalen-4-yloxy]propan-2-one (la) took place a cyclization, debenzylation and oxidation to form 9-substitued benzo[de]chromene-7,8-dione (2a) and 5-benzyl-9-substitued benzo[de]chromene-7,8-dione (3a). The mechanisms for these reactions were discussed.
文摘Stereoselective functionalization at C-2 and C-3 of the gibberellin skeleton was achieved via an intramolecular free radical cyclization approach using a tethered C-19 halomethyl ester as the radical precursor.
文摘Ferric chloride catalyzes the isomerization and cyclization of geraniol, linalool and nerol in acetonitrile giving a-terpineol in good to high yields.
基金supported by the National Natural Science Foundation of China(21878038)the Natural Science Foundation of Liaoning Province(20170540156)the Program for Changjiang Scholars and Innovative Research Team in University(IRT-17R14)~~
文摘The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative cyclization of a variety of alkynic hydrazones with carbon dioxide to produce the corresponding 1,3,4-oxadiazin-2-ones under mild reaction conditions. In this reaction, silver(I) salts play a π-Lewis acid role for the highly efficient activation of the alkyne moiety in the hydrazone substrates. Single-crystal X-ray analysis and NOE experiments confirm that the newly formed oxadiazinone products exhibit Z configuration. Based on control experiments and NMR studies, a mechanism including the formation of a reactive carbazate intermediate, electrophilic cyclization, and subsequent protonation is proposed. This study offers an efficient and atom- economical method for the synthesis of biologically important 1,3,4-oxadiazin-2-ones.
文摘new method to synthesize heterocycle-fused troponoid compounds by oxidizing azocoupling products of 3-isopropenyltropolone and 3-cinnamoyltropolone with bromine in the presence of pyridine was reported for the first time. Reaction of azo-couping products of 3-isopropenyl tropolone 1a similar to f and 3-cinnamoyltropolone 3a similar to d with excess bromine afforded heterocycle-fused troponoid compounds 2a similar to f, 4a similar to d, respectively.
文摘A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excellent yields.
基金We thank the National Science Foundation of China for financial support (No.29472036).
文摘Substituted 2-halomethyl-2,3-dihydrobenzofurans were synthesized in one pot and in mild yield from substituted o-allylphenols with diacetoxyiodobenzene in the presence of 12 or Br2 in dry CH2Cl2 under reflux.
文摘The reaction of α-triazolyl-α, β-unsaturated ketones with phenyl hydrazine was studied. The result indicated that cyclization took place and new heterocyclic compounds of substituted 4,5-2H-pyrazoles were obtained, whose structures and conformation were characterized by 1H NMR, IR, MS, elemental analysis and X-ray diffraction.
基金This work is supported by the National Natural Science Foundation of China (grant No: 20372056)a Research Fund from the Royal Society of Chemistry. UK.
文摘A novel macrolactonization method was developed using a chiral β-lactam as the template. This novel method features that the macrocyclization is simultaneously achieved while a TBS protected hydroxy group is deprotected.
文摘Intramolecular cyclization of A catalyzed by IDA in benzene or THF yields two γ-lactams through C-alkylation and one δ-and one 7-membered lactam by O-alkylation.
基金financial support from the National Outstanding Youth Fund(No.29925204)
文摘An effective approach for the construction of the decalin ring skeleton of labdane diterpenoids was developed based on a key biomimetic cationic polyene cyclization of an epoxy allylsilane precursor. The synthetic approach demonstrated here would be useful in the enantioselective and diastereoselective total synthesis of natural labdane diterpenoids in general.
基金the National Natural Science Foundation of China (No. 20332050)
文摘The Lewis acid mediated polystyrene supported selenium cyclization of chalcones and oxidative cleavage of selenium resins flavonoids in good yields and purities have been reported. induced intramolecular gave the corresponding
文摘Some new benzimidazoles and benzoxazoles have been prepared under mild condition by oxidative cyclization of arylaldehyde witho-phenylenediamine ando-aminophenol using potassium ferricyanide as oxidant
基金This work is supported by the National Natural Science Foundation of China (No. 20442004 10576002).
文摘The cyclization reaction of D-aspartic acid was studied, the carboxyl groups of D-aspartic acid were protected by benzyl alcohol to give compound D-dibenzyl aspartate. Then (4R)-benzyl azetidine-2-one-4-carboxylate and meso-3,6-disubstituted piperazine-2,5-diones were synthesized via intramolecular cyclization and intermolecular cycfization of D-dibenzyl aspartate, respectively, and their structures were confirmed by ^1 H NMR and MS. Both cyclization reaction conditions were also investigated in detail.
基金the Natural Science Foundation of Yunnan Province(2014FA008 and 2015FB167)the Program for Changjiang Scholars and Innovative Research Team in University(IRT13095).
文摘A highly efficient and direct approach was developed to construct the structurally diverse spirooxindole skeleton,which is an important basic motif in natural products.Both the 3,30-pyrrolidonyl spirooxindoles and spiroindolin-2-one dlactones were 2smoothly obtained by the intramolecular Dieckmann cyclization of oxindoles in excellent yield under mild conditions.
文摘The major products of carbonium cyclization of 1 are 2 and 3;2 is unstable and undergoes aerial oxidation to give 4.A similar product(6)from 5 is somehow stabilized by the extra ben- zoyloxy group(or OH)and can be stored without deterioration.