Allyldialkyltelluronium bromides were treated with aromatic amines in 1,2-dichloroethane,readily giving allyl aryl amines in excel- lent yields.This method provides a convenient one-pot reaction for the synthesis of a...Allyldialkyltelluronium bromides were treated with aromatic amines in 1,2-dichloroethane,readily giving allyl aryl amines in excel- lent yields.This method provides a convenient one-pot reaction for the synthesis of allylic amines.展开更多
In the presence of catalytic amount of In(OTf)3 (10 mol%), a series of aldimines reacted with tetraallyltin in a 2:1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom effici...In the presence of catalytic amount of In(OTf)3 (10 mol%), a series of aldimines reacted with tetraallyltin in a 2:1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom efficiency was achieved under mild reaction conditions and a new protocol (allyl)4Sn/In(OTf)3 for simple imines was developed.展开更多
Allylation of terminal epoxides(1)to give the homoallylic alcohols(2)and bishomoallylic alcohols(3)can be carried out successfully by allyl bromide and metallic zinc or tin.The effect of substituents on epoxides was s...Allylation of terminal epoxides(1)to give the homoallylic alcohols(2)and bishomoallylic alcohols(3)can be carried out successfully by allyl bromide and metallic zinc or tin.The effect of substituents on epoxides was studied.展开更多
A Ru(II)-catalyzed ortho allylation reaction of N-aryl-7-azaindole with readily available 2-methylidene cyclic carbonate has been developed.This reaction is an effective pathway for synthesizing 7-azaindole derivative...A Ru(II)-catalyzed ortho allylation reaction of N-aryl-7-azaindole with readily available 2-methylidene cyclic carbonate has been developed.This reaction is an effective pathway for synthesizing 7-azaindole derivatives with a wide scope of substrates and high yields.In addition,the method can be extended to the allylation of other heterocyclic compounds and several cyclic carbonates,highlighting the practicality of this strategy for synthesis.展开更多
Oxazolones are structural subunits in numerous natural products and designed molecules with substantial pharmacological properties.Here,a palladium-catalyzed chemodivergent regio-and enantioselective allylic alkylatio...Oxazolones are structural subunits in numerous natural products and designed molecules with substantial pharmacological properties.Here,a palladium-catalyzed chemodivergent regio-and enantioselective allylic alkylation of 4-or 5-substituted oxazol-2(3H)-ones with Morita-Baylis-Hillman(MBH)adducts has been developed using a spiroketal-based diphosphine as the ligand(50 examples).Interestingly,4-substituted oxazol-2(3H)-ones acted as a C-nucleophiles in the reaction to afford a range of chiral 4,5-substituted oxazol-2(3H)-ones in high yields(72-99%)with good to excellent chemo-,regio-,and enantioselectivities(C/N 95:5->99:1,b/l 91:9->99:1,85-98%ee).When a N-nucleophile was used under otherwise identical conditions,5-substituted oxazol-2(3H)-ones delivered a range of chiral 3,5-substituted oxazol-2(3H)-ones in high yields(68-98%)with good regio-and enantioselectivities(b/l 71:29-91:9,66-94%ee).The synthesis can be readily performed on gram scale under fairly low catalyst loadings,and the utility of the protocol was showcased in the facile transformation of the products into more elaborate chiral molecules.展开更多
Tin mediated allylation of aldehydes or ketones in distilled water gives rise to the corresponding homoallyl alcohols in high yield without assistance such as heat, supersonic and acidic media.
Monofluoroalkenes are important and versatile privileged components in pharmacologically relevant molecules.Here,we report a method for the selective construction of these compounds in a diversity-oriented fashion thr...Monofluoroalkenes are important and versatile privileged components in pharmacologically relevant molecules.Here,we report a method for the selective construction of these compounds in a diversity-oriented fashion through regiodivergent cross-coupling of gem-difluorocyclopropanes with allylboronates by employing a palladium catalyst with two different ligands,in which gem-difluorocyclopropanes were used as allyl electrophiles by C—C and C—F bond activation.In the presence of 2-biphenylyl(diphenyl)phosphine as ligand,the linear-selective allyl–allyl bond formation is highly obtained,while utilizing the sterically hindered BrettPhos(dicyclohexyl[3,6-dimethoxy-2',4',6'-tris(1-methylethyl)[1,1'-biphenyl]-2-yl]phosphine)as the ligand favors the generation of the branched-selective product.Experimental and computational studies investigated the key steps of the cross-coupling reactions,revealing the origin of the ligand-controlled regiodivergence.展开更多
Comprehensive Summary Asymmetric catalytic allylation of halo-substituted ketones and ketoesters was accomplished to yield a number of homoallylic tertiary alcohols in excellent reactivity and enantioselectivity.In th...Comprehensive Summary Asymmetric catalytic allylation of halo-substituted ketones and ketoesters was accomplished to yield a number of homoallylic tertiary alcohols in excellent reactivity and enantioselectivity.In the presence of chiral In^(Ⅲ)/N,N-dioxide catalyst,unusual α-selective allylation ofγ-substituted potassium allyltrifluoroborates to ketones was demonstrated.The control experiments and DFT calculation reveal that chiral In^(Ⅲ)/N,N'-dioxide catalyst plays dual-tasking roles:the formation of allylindium species via transmetalation and Lewis acid activation.Apossiblereaction pathwaywas provided tounderstandα-selectivity overy-selectivity.展开更多
[Cp^(*)Co(CO)l_(2)]effectively catalyzes pyridyl-directed C-H allylation of arenes with allylic amines in the presence of AgOAc and CF_(3)COOAg.The reaction features ortho-position monoallylation of 2-pyridylarenes,gi...[Cp^(*)Co(CO)l_(2)]effectively catalyzes pyridyl-directed C-H allylation of arenes with allylic amines in the presence of AgOAc and CF_(3)COOAg.The reaction features ortho-position monoallylation of 2-pyridylarenes,giving the allylated arenes in moderate to high yields.A range of functional groups including OMe,Me,Ph,F,Cl,Br,CF_(3),C(0)Me,COOEt,and COOH groups are tolerated.Pyrim-idyl-directed C-H allylation of arenes were also performed under the same conditions.Reaction of 2-phenylpyrimidine,2-(4-methoxyphenyl)pyrimidine/and 2-(3-fluorophenyl)pyrimidine leads to a mixture of ortho-position mono-and bisallylation products.Reaction of other 2-(substituted aryl)pyrimidines resulted in ortho-position monoallylation products.展开更多
A series of novel axially chiral 2,2'-bipyridine N,N'-dioxides bearing C1 or C2-symmetry have been synthesized by the use of enantiopure a-amino acids as chiral sources. The absolute stereochemistry of the axial chi...A series of novel axially chiral 2,2'-bipyridine N,N'-dioxides bearing C1 or C2-symmetry have been synthesized by the use of enantiopure a-amino acids as chiral sources. The absolute stereochemistry of the axial chirality of these organocatalysts has been clearly assigned by means of CD measurements together with literature protocols. The reactivities and enantioselectivities of these organocatalysts have been examined in the reactions of aromatic aldehydes with allyltrichlorosilane, thus providing the desired products with moderate yields and enantioselectivies.展开更多
When treated with an alkoxide base like t-BuOK in aprotic solvent,N-di phenyl methyl imino oxindoles,made conveniently through condensation of corresponding isatins with N-di phenyl methyl amine,are deprotonated to fo...When treated with an alkoxide base like t-BuOK in aprotic solvent,N-di phenyl methyl imino oxindoles,made conveniently through condensation of corresponding isatins with N-di phenyl methyl amine,are deprotonated to form azaallyl anions.Allylation and alkylation of this type of intermediates proceed smoothly with diverse C-electrophiles.Acidic work up finishes 3-amino-3-allyl/alkyl oxindoles.The overall transformation equals to an umpolung process at the C3 of isatins.展开更多
The utilization of readily available amino acids,which is not only an oxygen nucleophile but also a nitrogen nucleophile,in palladium-catalyzed allylic substitution is realized under mild conditions.The chemoselectivi...The utilization of readily available amino acids,which is not only an oxygen nucleophile but also a nitrogen nucleophile,in palladium-catalyzed allylic substitution is realized under mild conditions.The chemoselectivity and multiple allylation are controlled by adjusting the reaction conditions.This represents the first example of this convenient access to valuable N,O-diallylated amino acids.Under the title conditions,a range of amino acids(α-,β-,γ-)and dipeptides can be readily converted in to the corresponding allylic products with excellent yields(67 examples,up to 99%yield)as well as good functional group tolerance.展开更多
Copper was found to be able to promote the SnCl2-mediated carbonyl allylation reactions in water, giving the corresponding homoallylic alcohol products in very high yields. Detailed studies showed that the reaction co...Copper was found to be able to promote the SnCl2-mediated carbonyl allylation reactions in water, giving the corresponding homoallylic alcohol products in very high yields. Detailed studies showed that the reaction could be applied to a variety of carbonyl compounds including those with hydroxyl, amino and nitro groups. It was also found that this reaction showed good regioselectivities for some substrates. Furthermore, carefully controled ex-periments and in situ NMR measurements provided important insights into the mechanism of the newly developed reaction.展开更多
1 Results The enantioselective addition of allylic organometallic reagents to aldehydes is a fundamental tool in organic synthesis.The high degree of both diastereo-and enantioselectivity gives the possibility to obta...1 Results The enantioselective addition of allylic organometallic reagents to aldehydes is a fundamental tool in organic synthesis.The high degree of both diastereo-and enantioselectivity gives the possibility to obtain a wide series of homoallylic alcohols,versatile intermediates in a great number of synthesis[1]. One of the most successful approaches is related to the discovery that organocatalytic activation of the nucleophilic allyltrichlorosilanes by means of neutral Lewis bases,such as formamides,...展开更多
Barbier allylation and Friedel-Crafts alkylation of (un)substituted benzaldehydes, allylbromide and phenols can be combined in a one-pot process in ionic liquid (BuPyC1/SnC12·2H2O) to directly synthesize 4-(...Barbier allylation and Friedel-Crafts alkylation of (un)substituted benzaldehydes, allylbromide and phenols can be combined in a one-pot process in ionic liquid (BuPyC1/SnC12·2H2O) to directly synthesize 4-(2-hydroxyphenyl)- 4-[(un)substituted phenyl]but-1-ene compounds, which were applied to the synthesis of 4-(substituted phenyl)- chromans through intramolecular cyclization reactions.展开更多
The benzylation and allylation of 4-nitrobenzaldehyde (1) could be controlled chemoselectively by using different phase transfer catalyst (FTC) and different metal catalysts. And then, benzylation and allylation of 1 ...The benzylation and allylation of 4-nitrobenzaldehyde (1) could be controlled chemoselectively by using different phase transfer catalyst (FTC) and different metal catalysts. And then, benzylation and allylation of 1 with various organic halides has been realized in high yields in aqueous media.展开更多
A series of aminophosphine ligands was synthesized from 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN). Their asymmetric induction efficiency was examined for silver(I) catalyzed enantioselective allylation reaction of ...A series of aminophosphine ligands was synthesized from 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN). Their asymmetric induction efficiency was examined for silver(I) catalyzed enantioselective allylation reaction of benzaldehyde with allyltributyltin. Under the optimized reaction conditions, quantitative yield as well as moderate ee value (54.5% ee) of product was achieved by the catalysis with silver(I)/3 complex. The effects of the binaphthyl backbone and the substitutes situated at chelating N, P atoms on enantioselectivity of the reaction were also discussed.展开更多
of main observation and conclusion A new class of indole-based allylic donors have been designed and developed for palladium-catalyzed decarboxylative allylations.In addition,the first application of these indole-base...of main observation and conclusion A new class of indole-based allylic donors have been designed and developed for palladium-catalyzed decarboxylative allylations.In addition,the first application of these indole-based allylic donors in palladium-catalyzed decarboxylative[3+2]cydoaddition and allylic amination has been achieved by reacting with isocyanates and sulfonyl amines,respectively.This approach represents the first design of indole-based allylic donors,which is helpful for settling the challenge of designing and developing new class of heterocycle-based allylic donors for Pd-catalyzed decarboxylative allylation reactions.Moreover,the application of this new class of allylic donors in cycloadditions and substitutions will add new contents to the research field of decarboxylative allylation.展开更多
文摘Allyldialkyltelluronium bromides were treated with aromatic amines in 1,2-dichloroethane,readily giving allyl aryl amines in excel- lent yields.This method provides a convenient one-pot reaction for the synthesis of allylic amines.
基金the National Natural Science Foundation of China(Nos.20421202,20372033)for financialsupport.
文摘In the presence of catalytic amount of In(OTf)3 (10 mol%), a series of aldimines reacted with tetraallyltin in a 2:1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom efficiency was achieved under mild reaction conditions and a new protocol (allyl)4Sn/In(OTf)3 for simple imines was developed.
文摘Allylation of terminal epoxides(1)to give the homoallylic alcohols(2)and bishomoallylic alcohols(3)can be carried out successfully by allyl bromide and metallic zinc or tin.The effect of substituents on epoxides was studied.
基金supported by the Natural Science Foundation of Shandong Province(ZR2019BB011)the Scientific Research Foundation of Qingdao University of Science&Technology(010029022).
文摘A Ru(II)-catalyzed ortho allylation reaction of N-aryl-7-azaindole with readily available 2-methylidene cyclic carbonate has been developed.This reaction is an effective pathway for synthesizing 7-azaindole derivatives with a wide scope of substrates and high yields.In addition,the method can be extended to the allylation of other heterocyclic compounds and several cyclic carbonates,highlighting the practicality of this strategy for synthesis.
基金financial supports from the National Key R&D Program of China(grant nos.2022YFA1503702 and 2021YFF0701602)NSFC(grant nos.22231011 and 22271303).
文摘Oxazolones are structural subunits in numerous natural products and designed molecules with substantial pharmacological properties.Here,a palladium-catalyzed chemodivergent regio-and enantioselective allylic alkylation of 4-or 5-substituted oxazol-2(3H)-ones with Morita-Baylis-Hillman(MBH)adducts has been developed using a spiroketal-based diphosphine as the ligand(50 examples).Interestingly,4-substituted oxazol-2(3H)-ones acted as a C-nucleophiles in the reaction to afford a range of chiral 4,5-substituted oxazol-2(3H)-ones in high yields(72-99%)with good to excellent chemo-,regio-,and enantioselectivities(C/N 95:5->99:1,b/l 91:9->99:1,85-98%ee).When a N-nucleophile was used under otherwise identical conditions,5-substituted oxazol-2(3H)-ones delivered a range of chiral 3,5-substituted oxazol-2(3H)-ones in high yields(68-98%)with good regio-and enantioselectivities(b/l 71:29-91:9,66-94%ee).The synthesis can be readily performed on gram scale under fairly low catalyst loadings,and the utility of the protocol was showcased in the facile transformation of the products into more elaborate chiral molecules.
文摘Tin mediated allylation of aldehydes or ketones in distilled water gives rise to the corresponding homoallyl alcohols in high yield without assistance such as heat, supersonic and acidic media.
基金the National Natural Science Foundation of China(Grants 22025104,21972064 and 21901111)the Fundamental Research Funds for the Central Universities for their financial support(Grant 020514380254)The project was also supported by Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University.
文摘Monofluoroalkenes are important and versatile privileged components in pharmacologically relevant molecules.Here,we report a method for the selective construction of these compounds in a diversity-oriented fashion through regiodivergent cross-coupling of gem-difluorocyclopropanes with allylboronates by employing a palladium catalyst with two different ligands,in which gem-difluorocyclopropanes were used as allyl electrophiles by C—C and C—F bond activation.In the presence of 2-biphenylyl(diphenyl)phosphine as ligand,the linear-selective allyl–allyl bond formation is highly obtained,while utilizing the sterically hindered BrettPhos(dicyclohexyl[3,6-dimethoxy-2',4',6'-tris(1-methylethyl)[1,1'-biphenyl]-2-yl]phosphine)as the ligand favors the generation of the branched-selective product.Experimental and computational studies investigated the key steps of the cross-coupling reactions,revealing the origin of the ligand-controlled regiodivergence.
基金This work is supported by the National Natural Science Foundation of China(No.21890723)Sichuan University(2020SCUNL204).
文摘Comprehensive Summary Asymmetric catalytic allylation of halo-substituted ketones and ketoesters was accomplished to yield a number of homoallylic tertiary alcohols in excellent reactivity and enantioselectivity.In the presence of chiral In^(Ⅲ)/N,N-dioxide catalyst,unusual α-selective allylation ofγ-substituted potassium allyltrifluoroborates to ketones was demonstrated.The control experiments and DFT calculation reveal that chiral In^(Ⅲ)/N,N'-dioxide catalyst plays dual-tasking roles:the formation of allylindium species via transmetalation and Lewis acid activation.Apossiblereaction pathwaywas provided tounderstandα-selectivity overy-selectivity.
基金the National Natural Science Foundation of China(No.21372212)the National Basic Research Program of China(No.2015CB856600)is greatly acknowledged.
文摘[Cp^(*)Co(CO)l_(2)]effectively catalyzes pyridyl-directed C-H allylation of arenes with allylic amines in the presence of AgOAc and CF_(3)COOAg.The reaction features ortho-position monoallylation of 2-pyridylarenes,giving the allylated arenes in moderate to high yields.A range of functional groups including OMe,Me,Ph,F,Cl,Br,CF_(3),C(0)Me,COOEt,and COOH groups are tolerated.Pyrim-idyl-directed C-H allylation of arenes were also performed under the same conditions.Reaction of 2-phenylpyrimidine,2-(4-methoxyphenyl)pyrimidine/and 2-(3-fluorophenyl)pyrimidine leads to a mixture of ortho-position mono-and bisallylation products.Reaction of other 2-(substituted aryl)pyrimidines resulted in ortho-position monoallylation products.
基金We thank Beijing Municipal Commission of Edu- cation (No. JC015001200902), Beijing Municipal Natu- ral Science Foundation (Nos. 710201, 2122008), Basic Research Foundation of Beijing University of Technol- ogy (X40 15001201101), Funding Project for Academic Human Resources Development in Institutions ofHigher Learning Under the Jurisdiction of Beijing Municipality (No. PHR201008025), Doctoral Scientific Research Start-up Foundation of Beijing University of Technology (No. 52015001200701) for financial sup- ports.
文摘A series of novel axially chiral 2,2'-bipyridine N,N'-dioxides bearing C1 or C2-symmetry have been synthesized by the use of enantiopure a-amino acids as chiral sources. The absolute stereochemistry of the axial chirality of these organocatalysts has been clearly assigned by means of CD measurements together with literature protocols. The reactivities and enantioselectivities of these organocatalysts have been examined in the reactions of aromatic aldehydes with allyltrichlorosilane, thus providing the desired products with moderate yields and enantioselectivies.
基金the National Natural Science Foundation of China(No.21672027)for financial supportsupported by High-Level Entrepreneurial Talent Team of Jiangsu Province(No.2017-37)。
文摘When treated with an alkoxide base like t-BuOK in aprotic solvent,N-di phenyl methyl imino oxindoles,made conveniently through condensation of corresponding isatins with N-di phenyl methyl amine,are deprotonated to form azaallyl anions.Allylation and alkylation of this type of intermediates proceed smoothly with diverse C-electrophiles.Acidic work up finishes 3-amino-3-allyl/alkyl oxindoles.The overall transformation equals to an umpolung process at the C3 of isatins.
基金financial support from the National Natural Science Foundation of China(No.21602144)the Science and Technology Program of Sichuan Province(No.2018JY0485)Scientific Research Project of Education Department of Hubei Province(Nos.Q20211503,B2020057)。
文摘The utilization of readily available amino acids,which is not only an oxygen nucleophile but also a nitrogen nucleophile,in palladium-catalyzed allylic substitution is realized under mild conditions.The chemoselectivity and multiple allylation are controlled by adjusting the reaction conditions.This represents the first example of this convenient access to valuable N,O-diallylated amino acids.Under the title conditions,a range of amino acids(α-,β-,γ-)and dipeptides can be readily converted in to the corresponding allylic products with excellent yields(67 examples,up to 99%yield)as well as good functional group tolerance.
基金Project supported by Chinese Academy of Sciences (No. KJCXZ-SW-04) and the National Natural Science Foundation of China (No. 20332020).
文摘Copper was found to be able to promote the SnCl2-mediated carbonyl allylation reactions in water, giving the corresponding homoallylic alcohol products in very high yields. Detailed studies showed that the reaction could be applied to a variety of carbonyl compounds including those with hydroxyl, amino and nitro groups. It was also found that this reaction showed good regioselectivities for some substrates. Furthermore, carefully controled ex-periments and in situ NMR measurements provided important insights into the mechanism of the newly developed reaction.
文摘1 Results The enantioselective addition of allylic organometallic reagents to aldehydes is a fundamental tool in organic synthesis.The high degree of both diastereo-and enantioselectivity gives the possibility to obtain a wide series of homoallylic alcohols,versatile intermediates in a great number of synthesis[1]. One of the most successful approaches is related to the discovery that organocatalytic activation of the nucleophilic allyltrichlorosilanes by means of neutral Lewis bases,such as formamides,...
文摘Barbier allylation and Friedel-Crafts alkylation of (un)substituted benzaldehydes, allylbromide and phenols can be combined in a one-pot process in ionic liquid (BuPyC1/SnC12·2H2O) to directly synthesize 4-(2-hydroxyphenyl)- 4-[(un)substituted phenyl]but-1-ene compounds, which were applied to the synthesis of 4-(substituted phenyl)- chromans through intramolecular cyclization reactions.
文摘The benzylation and allylation of 4-nitrobenzaldehyde (1) could be controlled chemoselectively by using different phase transfer catalyst (FTC) and different metal catalysts. And then, benzylation and allylation of 1 with various organic halides has been realized in high yields in aqueous media.
文摘A series of aminophosphine ligands was synthesized from 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN). Their asymmetric induction efficiency was examined for silver(I) catalyzed enantioselective allylation reaction of benzaldehyde with allyltributyltin. Under the optimized reaction conditions, quantitative yield as well as moderate ee value (54.5% ee) of product was achieved by the catalysis with silver(I)/3 complex. The effects of the binaphthyl backbone and the substitutes situated at chelating N, P atoms on enantioselectivity of the reaction were also discussed.
基金We are grateful for financial support from NSFC(Nos.21772069,21831007 and 21702077)the Natural Science Founda-tion of Jiangsu Province(No.BK20170227)Six Kinds of Talents Project of Jiangsu Province(No.SWYY-025).
文摘of main observation and conclusion A new class of indole-based allylic donors have been designed and developed for palladium-catalyzed decarboxylative allylations.In addition,the first application of these indole-based allylic donors in palladium-catalyzed decarboxylative[3+2]cydoaddition and allylic amination has been achieved by reacting with isocyanates and sulfonyl amines,respectively.This approach represents the first design of indole-based allylic donors,which is helpful for settling the challenge of designing and developing new class of heterocycle-based allylic donors for Pd-catalyzed decarboxylative allylation reactions.Moreover,the application of this new class of allylic donors in cycloadditions and substitutions will add new contents to the research field of decarboxylative allylation.