An uncatalyzed and easily accessible synthetic approach for the preparation of 3-aroylindoles was investigated using nitrosoarenes and aromatic terminal ethynyl ketones. Indole derivatives were produced in good yields...An uncatalyzed and easily accessible synthetic approach for the preparation of 3-aroylindoles was investigated using nitrosoarenes and aromatic terminal ethynyl ketones. Indole derivatives were produced in good yields and excellent regioselectivity. Functionalizations of the indole products were carried out affording highly valuable and versatile compounds. The indolization protocol was studied as a fundamental step for the preparation of pravadoline and 1-butyl-3-(1-naphthoyl)indole (JWH-073), bioactive molecules showing antinociceptic properties.展开更多
Ligand-mediated nickel-catalyzed asymmetric hydrogenation of alkynone imines has been achieved. By using Ni(OAc)_2·4H_2O/(S,S)-Ph-BPE complex as a catalyst, the chemo-and enantioselective hydrogenation of alkynon...Ligand-mediated nickel-catalyzed asymmetric hydrogenation of alkynone imines has been achieved. By using Ni(OAc)_2·4H_2O/(S,S)-Ph-BPE complex as a catalyst, the chemo-and enantioselective hydrogenation of alkynone imines occurred efficiently to afford chiral propargyl amines with high yields and excellent enantioselectivities(up to 99% yield, >99% ee), leaving the readily reducible alkynyl group intact. Both the C=N and C≡C bonds of alkynone imines were hydrogenated efficiently in the presence of Ni(OAc)_2·4H_2O and Josiphos SL-J011-1, furnishing unfunctionalized chiral imines efficiently(up to 99% yield, >99% ee).The(Z)-allylamines and(E)-allylamines were also efficiently prepared from alkynone imines by the combination of the different catalytic systems. The preliminary mechanism study revealed that the reduction of alkynone imines was a stepwise process and the C=N bonds were preferably hydrogenated in the complete reduction of alkynone imines. The synthetic utility of this method was demonstrated by its application in the late-stage modification of the antiviral drug Zidovudine and the concise synthesis of chiral dibenzoazepine.展开更多
The reaction of the 16e half-sandwich complex Cp*Co(S2C2B10H10) (1) (Cp* = pentamethylcyclopentadienyl) with excess methyl acetylene monocarboxylate, HC≡C-CO2Me, affords the 18e complexes 2-6. Compound 2 bears a B-CH...The reaction of the 16e half-sandwich complex Cp*Co(S2C2B10H10) (1) (Cp* = pentamethylcyclopentadienyl) with excess methyl acetylene monocarboxylate, HC≡C-CO2Me, affords the 18e complexes 2-6. Compound 2 bears a B-CH2 unit in which B-substitution occurs in the B(3)/B(6) position of the ortho-carborane cage. Complexes 3-6 are geometrical isomers, in which the alkyne is twofold inserted into one of the Co-S bonds in all the four possible ways. Treatment of 1 with excess 3-butyn-2-one or phenyl ethynyl ketone, HC≡C-C(O)R (R = Me, Ph), at ambient temperature leads to the 18e complexes 7-10, respectively, with two alkynes inserted into one of the Co-S bonds. All the new complexes were fully characterized by spectroscopic techniques and elemental analysis. The solid-state structures of 2, 3, 5, 7, 8, 9 and 10 were further characterized by X-ray structural analysis.展开更多
Reaction of [1S,2S-(Ts-diphen)Ru(II)(p-cymene)] (1S,2S-Ts-diphen=1S,2S-N-tosyl-1,2-diphenylethylenedi- amine) and 2-hydroxy-2-methyl-non-3-yn-5-one under transfer hydrogenation condition gave a ruthenium complex beari...Reaction of [1S,2S-(Ts-diphen)Ru(II)(p-cymene)] (1S,2S-Ts-diphen=1S,2S-N-tosyl-1,2-diphenylethylenedi- amine) and 2-hydroxy-2-methyl-non-3-yn-5-one under transfer hydrogenation condition gave a ruthenium complex bearing a 2,5-dihydrofuran moiety. The complex was characterized and a possible mechanism for the formation of the complex was proposed.展开更多
Nickel/(S)-t-Bu-PHOX complex catalyzed asymmetric arylative cyclization of N-alkynones has been achieved, delivering 1,2,3,6-tetrahydropyridines containing a chiral tertiary alcohol in high yields and excellent enanti...Nickel/(S)-t-Bu-PHOX complex catalyzed asymmetric arylative cyclization of N-alkynones has been achieved, delivering 1,2,3,6-tetrahydropyridines containing a chiral tertiary alcohol in high yields and excellent enantioselectivities, which provides efficient access to chiral tetrahydropyridine and piperidine analogues.展开更多
Promoted by samarium diiodide in THF, the α,β-unsaturated alkynones were reduced to afford intermolecular reductive coupling products. The multiply substituted cyclopentadienes were prepared conveniently in good yie...Promoted by samarium diiodide in THF, the α,β-unsaturated alkynones were reduced to afford intermolecular reductive coupling products. The multiply substituted cyclopentadienes were prepared conveniently in good yields.展开更多
3-CF3 S substituted thioflavones and benzothiophenes were achieved via the reactions of AgSCF3 with methylthiolated alkynones and alkynylthioanisoles,respectively,promoted by persulfate.This protocol possesses good fu...3-CF3 S substituted thioflavones and benzothiophenes were achieved via the reactions of AgSCF3 with methylthiolated alkynones and alkynylthioanisoles,respectively,promoted by persulfate.This protocol possesses good functional group tolerance and high yields.Mechanistic studies suggested that a classic two-step radical process was involved,which includes addition of CF3 S radical to triple bond and cyclization with SMe moiety.展开更多
文摘An uncatalyzed and easily accessible synthetic approach for the preparation of 3-aroylindoles was investigated using nitrosoarenes and aromatic terminal ethynyl ketones. Indole derivatives were produced in good yields and excellent regioselectivity. Functionalizations of the indole products were carried out affording highly valuable and versatile compounds. The indolization protocol was studied as a fundamental step for the preparation of pravadoline and 1-butyl-3-(1-naphthoyl)indole (JWH-073), bioactive molecules showing antinociceptic properties.
基金supported by the National Natural Science Foundation of China (22071188, 21871212)the Open Foundation of CAS Key Laboratory of Molecular Recognition and Functionthe “Double First-Class” Project of Shihezi University。
文摘Ligand-mediated nickel-catalyzed asymmetric hydrogenation of alkynone imines has been achieved. By using Ni(OAc)_2·4H_2O/(S,S)-Ph-BPE complex as a catalyst, the chemo-and enantioselective hydrogenation of alkynone imines occurred efficiently to afford chiral propargyl amines with high yields and excellent enantioselectivities(up to 99% yield, >99% ee), leaving the readily reducible alkynyl group intact. Both the C=N and C≡C bonds of alkynone imines were hydrogenated efficiently in the presence of Ni(OAc)_2·4H_2O and Josiphos SL-J011-1, furnishing unfunctionalized chiral imines efficiently(up to 99% yield, >99% ee).The(Z)-allylamines and(E)-allylamines were also efficiently prepared from alkynone imines by the combination of the different catalytic systems. The preliminary mechanism study revealed that the reduction of alkynone imines was a stepwise process and the C=N bonds were preferably hydrogenated in the complete reduction of alkynone imines. The synthetic utility of this method was demonstrated by its application in the late-stage modification of the antiviral drug Zidovudine and the concise synthesis of chiral dibenzoazepine.
基金the National Natural Science Foundation of China (20925104,90713023,20771055,20721002)the Major State Basic Research Development Program of China (2006CB806104)the National Basic Research Program of China (2007CB925101,2010CB923303)
文摘The reaction of the 16e half-sandwich complex Cp*Co(S2C2B10H10) (1) (Cp* = pentamethylcyclopentadienyl) with excess methyl acetylene monocarboxylate, HC≡C-CO2Me, affords the 18e complexes 2-6. Compound 2 bears a B-CH2 unit in which B-substitution occurs in the B(3)/B(6) position of the ortho-carborane cage. Complexes 3-6 are geometrical isomers, in which the alkyne is twofold inserted into one of the Co-S bonds in all the four possible ways. Treatment of 1 with excess 3-butyn-2-one or phenyl ethynyl ketone, HC≡C-C(O)R (R = Me, Ph), at ambient temperature leads to the 18e complexes 7-10, respectively, with two alkynes inserted into one of the Co-S bonds. All the new complexes were fully characterized by spectroscopic techniques and elemental analysis. The solid-state structures of 2, 3, 5, 7, 8, 9 and 10 were further characterized by X-ray structural analysis.
基金Project supported by the National Natural Science Foundation of China (No. 20172067) the Chinese Academy of Sciences and the Shanghai Mu-nicipal Commission of Science and Technology.
文摘Reaction of [1S,2S-(Ts-diphen)Ru(II)(p-cymene)] (1S,2S-Ts-diphen=1S,2S-N-tosyl-1,2-diphenylethylenedi- amine) and 2-hydroxy-2-methyl-non-3-yn-5-one under transfer hydrogenation condition gave a ruthenium complex bearing a 2,5-dihydrofuran moiety. The complex was characterized and a possible mechanism for the formation of the complex was proposed.
基金financial support from the National Natural Science Foundation of China (Nos. 22071188, 21871212)the open foundation of CAS Key Laboratory of Molecular Recognition and Function, the "Double First-Class" Project of Shihezi University。
文摘Nickel/(S)-t-Bu-PHOX complex catalyzed asymmetric arylative cyclization of N-alkynones has been achieved, delivering 1,2,3,6-tetrahydropyridines containing a chiral tertiary alcohol in high yields and excellent enantioselectivities, which provides efficient access to chiral tetrahydropyridine and piperidine analogues.
基金theNationalNaturalScienceFoundationofChina (No .2 0 0 72 0 33)andtheSpecializedResearchFundfortheDoctoralProgramofHigherEducation
文摘Promoted by samarium diiodide in THF, the α,β-unsaturated alkynones were reduced to afford intermolecular reductive coupling products. The multiply substituted cyclopentadienes were prepared conveniently in good yields.
基金the National Natural Science Foundation of China(Nos.21991123,21677094)for financial support。
文摘3-CF3 S substituted thioflavones and benzothiophenes were achieved via the reactions of AgSCF3 with methylthiolated alkynones and alkynylthioanisoles,respectively,promoted by persulfate.This protocol possesses good functional group tolerance and high yields.Mechanistic studies suggested that a classic two-step radical process was involved,which includes addition of CF3 S radical to triple bond and cyclization with SMe moiety.
