Palladium-catalyzed Amination Of Aryl Chlorides Research Articles

Palladium-catalyzed amination of aryl chlorides and bromides with ammonium salts.

We report the palladium-catalyzed coupling of aryl halides with ammonia and gaseous amines as their ammonium salts. The coupling of aryl chlorides and ortho-substituted aryl bromides with ammonium sulfate forms anilines with higher selectivity for the primary arylamine over the diarylamine than couplings with ammonia in dioxane. The resting state for the reactions of aryl chlorides is different from the resting state for the reactions of aryl bromides, and this change in resting states is proposed to account for a difference in selectivities for reactions of the two haloarenes.

Efficient palladium-catalyzed amination of aryl chlorides using di(dicyclohexylamino)phenylphosphine as a PN2 ligand

The palladium-catalyzed amination of a variety of aryl chlorides has been accomplished by using di(dicyclohexylamino)phenylphosphine (1) as a bulky electron-rich monoaryl phosphine ligand. The optimized condition for the palladium-catalyzed amination of aryl chloride is the followings: aniline (3.0 mmol, 1.0 equiv), chlorobenzene (3.15 mmol, 1.05 equiv), ligand 1 (1 mol %, 0.03 mmol), KOtBu (4.5 mmol, 1.5 equiv), Pd2(dba)3 (1 mol %, 0.03 mmol), and toluene as solvent at reflux temperature. We report on couplings of various amines or chloroamines with chlorobenzenes and heteroaryl chloride.

ChemInform Abstract: An Efficient Palladium‐Catalyzed Amination of Aryl Chlorides in Presence of 1,3‐Bis‐(2,6‐diisopropylphenyl)imidazolinium Chloride.

ChemInformVolume 41, Issue 36 Isocyclic Compounds ChemInform Abstract: An Efficient Palladium-Catalyzed Amination of Aryl Chlorides in Presence of 1,3-Bis-(2,6-diisopropylphenyl)imidazolinium Chloride. Huafeng Shen, Huafeng Shen Coll. Pharm. Sci., Zhejiang Univ. Technol., Hangzhou, Zhejiang 310032, Peop. Rep. ChinaSearch for more papers by this authorZhong-Ping Zhang, Zhong-Ping Zhang Coll. Pharm. Sci., Zhejiang Univ. Technol., Hangzhou, Zhejiang 310032, Peop. Rep. ChinaSearch for more papers by this authorJing-Hua Li, Jing-Hua Li Coll. Pharm. Sci., Zhejiang Univ. Technol., Hangzhou, Zhejiang 310032, Peop. Rep. ChinaSearch for more papers by this author Huafeng Shen, Huafeng Shen Coll. Pharm. Sci., Zhejiang Univ. Technol., Hangzhou, Zhejiang 310032, Peop. Rep. ChinaSearch for more papers by this authorZhong-Ping Zhang, Zhong-Ping Zhang Coll. Pharm. Sci., Zhejiang Univ. Technol., Hangzhou, Zhejiang 310032, Peop. Rep. ChinaSearch for more papers by this authorJing-Hua Li, Jing-Hua Li Coll. Pharm. Sci., Zhejiang Univ. Technol., Hangzhou, Zhejiang 310032, Peop. Rep. ChinaSearch for more papers by this author First published: 12 August 2010 https://doi.org/10.1002/chin.201036060Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume41, Issue36September 7, 2010 RelatedInformation

Efficient Palladium-Catalyzed Amination of Aryl Chlorides Using Dicyclo­hexylamino[(2,6-dimethyl)morpholino]phenylphosphine as a PN2 Ligand

The palladium-catalyzed amination of aryl chlorides with various amines is accomplished using dicyclohexyl­amino[(2,6-dimethyl)morpholino]phenylphosphine as a bulky electron-rich monoaryl phosphine ligand. The optimized reaction conditions required the use of 1 mol% each of catalyst and ligand.

Efficient palladium catalysts for the amination of aryl chlorides: a comparative study on the use of phosphium salts as precursors to bulky, electron-rich phosphines

Alkyl-di-(1-adamantyl)phosphonium salts are practical ligand precursors for the palladium-catalyzed amination of aryl chlorides. In the presence of typically 0.5 mol% Pd(OAc) 2 and 1 mol% of ligand precursor a variety of activated and deactivated aryl chlorides can be aminated in good to excellent yield (73–99%). Applying optimized conditions catalyst turnover numbers up to 10,000 have been achieved.

Rapid palladium-catalyzed aminations of aryl chlorides with aliphatic amines under temperature-controlled microwave heating

Rapid Buchwald–Hartwig amination of electron neutral and rich aryl chlorides and bromides have been achieved using temperature-controlled microwave heating. Primary and secondary aliphatic amines can be coupled with these substrates in good yields within a reaction time of only 10 min.

Aqueous hydroxide as a base for palladium-catalyzed amination of aryl chlorides and bromides.

The amination of aryl halides in the presence of inexpensive and air-stable alkali metal hydroxide bases and Pd[P(t-Bu)3]2 as catalyst gave arylamines in high yields. The reactions were conducted with a catalytic amount of cetyltrimethylammonium bromide as phase-transfer agent and either aqueous hydroxide or solid hydroxide in the presence of water. This combination of alkali metal hydroxide base, H2O, and the ammonium salt performed as well as NaO-t-Bu in the amination of p-chlorotoluene with dibutylamine. Hydroxide base was suitable for reactions of a wide range of aryl chlorides and bromides with aliphatic and aromatic amines. Some functional groups that were intolerant of tert-butoxide base, such as esters, enolizable ketones, nitriles, and nitro groups, were tolerated by the combination of hydroxide base, H2O, and cetyltrimethylammonium bromide in toluene solvent.

A new improved catalyst for the palladium-catalyzed amination of aryl chlorides

The catalytic amination of aryl chlorides is an interesting subject for the fine chemical industry due to the importance of anilines as building blocks for pharmaceuticals, agrochemicals and new materials. Here we report the application of our recently developed di(1-adamantyl)alkylphosphines for the palladium-catalyzed amination of non-activated aryl chlorides. In general, excellent yields of amination products are obtained using 0.5 mol% of palladium(II)acetate and 1 mol% of di(1-adamantyl)- n-butylphosphine ( 12) in toluene at 120 °C. Remarkable results are obtained for the coupling of hindered amines with sterically congested aryl chlorides. Comparing the new catalyst system with previously reported best palladium catalysts we found in all cases improved yields of amination products in the presence of our ligands.

Simple, Efficient Catalyst System for the Palladium-Catalyzed Amination of Aryl Chlorides, Bromides, and Triflates

Palladium complexes supported by (o-biphenyl)P(t-Bu)(2) (3) or (o-biphenyl)PCy(2) (4) are efficient catalysts for the catalytic amination of a wide variety of aryl halides and triflates. Use of ligand 3 allows for the room-temperature catalytic amination of many aryl chloride, bromide, and triflate substrates, while ligand 4 is effective for the amination of functionalized substrates or reactions of acyclic secondary amines. The catalysts perform well for a large number of different substrate combinations at 80-110 degrees C, including chloropyridines and functionalized aryl halides and triflates using 0.5-1.0 mol % Pd; some reactions proceed efficiently at low catalyst levels (0.05 mol % Pd). These ligands are effective for almost all substrate combinations that have been previously reported with various other ligands, and they represent the most generally effective catalyst system reported to date. Ligands 3 and 4 are air-stable, crystalline solids that are commercially available. Their effectiveness is believed to be due to a combination of steric and electronic properties that promote oxidative addition, Pd-N bond formation, and reductive elimination.

General and efficient palladium-catalyzed aminations of aryl chlorides

Pd(dba) 2/Ligand A catalyst efficiently catalyzes the aminations of a variety of aryl chlorides with a variety of amines in high rates, selectivities, and isolated yields.

Palladium-catalyzed amination of aryl chlorides

Pd(PCy 3)Cl 2 (Cy = cyclohexyl) catalyzed the reaction of aryl chlorides and secondary amines in the presence of NaO tBu to give the corresponding aryl amines in good to excellent yields. In some of the reactions, an excess amount of aryl chloride ( aryl chloride amine = 2 ) improved the yields.

First palladium-catalyzed aminations of aryl chlorides

The palladium-catalyzed coupling reaction of aryl chlorides with various amines has been studied for the first time. Crucial for the success of this CN bond forming reaction is the use of potassium tert-butoxide as base. Turn over numbers up to 900 and yields up to 80% have been obtained.