Arylation of adamantanamines: V. Palladium-catalyzed amination of isomeric chloroquinolines with diamines of the adamantane series

Palladium-catalyzed arylation of diamines of the adamantane series with isomeric 2-, 4-, and 6-chloroquinoline was studied, and optimal conditions for the synthesis of the corresponding N,N′-diaryl derivatives were found. N,N-Diarylation products of primary amino groups in the diamines bearing 2-aminoethyl and 4-aminophenyl substituents were readily formed.     

Arylation of adamantanamines: VI. Palladium-catalyzed arylation of amines and diamines of the adamantane series with 3-bromopyridine

Palladium-catalyzed amination of 3-bromopyridine with amines of the adamantane series in the presence of Pd(dba)₂/L [L = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl or 2-dimethylamino-2′-dicyclohexylphosphinobiphenyl] gave the desired N-(pyridin-3-yl)-substituted amines in 74–97% yields. Diamines of the adamantane series reacted with 2 equiv of 3-bromopyridine in a complicated fashion to produce mono- and triaryl-substituted derivatives as by-products, while the yields of N,N′-diarylation products were 18–56%.     

Arylation of adamantanamines: IX. Copper(I)-catalyzed arylation of adamantane-containing amines

Copper(I)-catalyzed arylation of 14 adamantane-containing amines with iodobenzene, 1-fluoro-4-iodobenzene, 1-iodo-4-(trifluoromethyl)benzene, and 1-iodo-4-methoxybenzene has been studied under the conditions optimized previously. The yields of the N-arylation products have been shown to depend in a complicated manner on the amine structure, steric environment of the amino group, and substituent nature in iodobenzene.     

Arylation of adamantanamines: II. Palladium-catalyzed amination of dihalobenzenes with adamantylalkanamines

Palladium-catalyzed arylation of various (1-adamantyl)alkanamines with isomeric (ortho, meta, and para) bromochloro- and dibromobenzenes was studied. Optimal catalytic systems were found for the synthesis of mono- and diamination products, and the dependences of their yields on the nature of the initial amine and dihalobenzene and on the amount of base were examined. Side amination products were isolated, and paths of their formation were analyzed.     

Arylation of adamantanamines: VIII. Optimization of the catalytic system for copper-catalyzed arylation of adamantane-containing amines

Arylation of adamantane-containing amines with iodobenzene in the presence of copper(I) and copper(II) compounds and various N,N-, N,O- and O,O-bidentate ligands was studied. The best results were obtained using the catalytic system CuI–rac-BINOL [1,1′-bi(naphthalen-2-ol)] (10/20 mol %). Reactions with iodobenzene derivatives containing electron-donor and electron-withdrawing substituents in the para position to the iodine atom were carried out under the optimal conditions.     

Deamination of amines of adamantane series

Conclusions The deamination of 1-aminoadamantane, 1,3-diammoadamantane and 1-amino-3-adamantanol leads to the formation of the corresponding alcohols. The isomerization of the adamantane skeleton was not observed in all cases.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimlcheskaya, No. 10, pp. 2378–2379, October, 1973.     

Palladium-catalyzed arylation of cyclopentadienes

Cyclopentadiene and metallocenes, typically zirconocene dichloride, are suitable substrates for multiple arylations with aryl bromides in palladium-catalyzed reactions. Thus, various aryl bromides bearing either an electron-donating or an electron-withdrawing substituent can react with these substrates to afford the corresponding 1,2,3,4,5-pentaaryl-1,3-cyclopentadienes in a single preparative step. Derivatives of cyclopentadiene, including di- and trisubstituted cyclopentadienes, and indene are arylated in a similar fashion.     

Palladium-catalyzed arylation of electron-rich heterocycles with aryl chlorides

[reaction: see text] Palladium-catalyzed C-H activation: cheap aryl chlorides can now be used for the arylation of a wide variety of electron-rich heterocycles. The key to the success of this reaction is the use of a bulky, electron-rich phosphine ligand. No copper additives are needed.     

Palladium-catalyzed direct arylation of N-heteroarenes with arylsulfonyl hydrazides

Hydrazides applied: A palladium-catalyzed direct C?H arylation of heteroarenes, with arylsulfonyl hydrazides as the arylating reagents, has been developed. The reaction is chemoselective, in that arylsulfonyl hydrazides containing halogen substituents can be employed without participation of the halogen substituent in the reaction. The method offers a straightforward approach to a variety of aryl-heteroaryl compounds.     

Palladium-catalyzed desulfitative arylation of sulfonamides with sodium arylsulfinates

A Pd(II)-catalyzed desulfitative arylation protocol between sulfonamides and sodium arylsulfinates was herein reported. The direct arylation reaction was successfully achieved by a Pd(II)/Ag(I)-mediated system without participation of any external ligands with a release of SO₂. And different N-aryl sulfonamides were obtained readily in up to 86% yields, exhibiting good functional groups tolerance (25 examples).     

Palladium-catalyzed benzylic arylation of N-benzylxanthone imine

The direct benzylic arylation of N-benzylxanthone imine with aryl chloride proceeds under palladium catalysis, yielding the corresponding coupling product. The product is readily transformed to benzhydrylamine. Taking into consideration that the imine is readily available from benzylic amine, the overall transformation represents a formal cross-coupling reaction of aryl halide with alpha-aminobenzyl metal.     

Palladium-catalyzed desulfitative arylation of azoles with arylsulfonyl hydrazides

Palladium-catalyzed desulfitative and denitrogenative arylation of azoles with arylsulfonyl hydrazides has been achieved. A broad scope of azoles and arylsulfonyl hydrazides has been used to produce arylated azoles in high yields.     

Palladium-catalyzed direct arylation of thiazoles with aryl bromides

Thiazole, 2-phenyl or -alkyl substituted one and benzothiazole are efficiently arylated with aryl bromides at the 2- and/or 5-position(s) in the presence of Pd(OAc)₂ and a bulky phosphine ligand using Cs₂CO₃ as base. 2-Phenyl-5-thiazolecarboxanilide undergoes successive diarylation at the 4- and 5-positions accompanied by decarbamoylation.     

Palladium-catalyzed benzylic C(sp3)–H carbonylative arylation of azaarylmethyl amines with aryl bromides

A highly selective palladium-catalyzed carbonylative arylation of weakly acidic benzylic C(sp³)–H bonds of azaarylmethylamines with aryl bromides under 1 atm of CO gas has been achieved. This work represents the first examples of use of such weakly acidic pronucleophiles in this class of transformations. In the presence of a NIXANTPHOS-based palladium catalyst, this one-pot cascade process allows a range of azaarylmethylamines containing pyridyl, quinolinyl and pyrimidyl moieties and acyclic and cyclic amines to undergo efficient reactions with aryl bromides and CO to provide α-amino aryl-azaarylmethyl ketones in moderate to high yields with a broad substrate scope and good tolerance of functional groups. This reaction proceeds via in situ reversible deprotonation of the benzylic C–H bonds to give the active carbanions, thereby avoiding prefunctionalized organometallic reagents and generation of additional waste. Importantly, the operational simplicity, scalability and diversity of the products highlight the potential applicability of this protocol.

Introduced is a method for the deprotonative carbonylation of azaarylmethyl amines with aryl bromides. The reaction employs a Pd(NIXANTPHOS)-based catalyst and takes place under 1 atm CO.     

乙烯基膦酸酯的钯催化芳基化和烯基化反应

本文报道乙烯基膦酸酯在钯催化下的芳基化和烯基化反应,乙烯基膦酸酯与芳基溴化合物在钯催化下反应,可顺利地生成相应的E式2-芳基取代乙烯基膦酸酯(6,7).操作简便,反应条件温和,产率中平,是合成2-芳基取代乙烯基膦酸酯较好的方法.测定了不同取代芳基乙烯基膦酸二乙酯的^31P NMRδ值,它们与Hammett取代基常数σ之间有较好的线性关系.乙烯基膦酸酯亦能与烯基溴化合物反应,生成相应的取代1,3-二烯基膦酸酯(10),但反应时间较长,产率较低,由NMR推定了6,7和10的构型。     

Palladium-catalyzed oxidative carbocyclization/arylation of enallenes

A stereoselective palladium-catalyzed oxidative carbocyclization/arylation of enallenes is described. The reaction shows wide tolerance toward highly functionalized arylboronic acids and results in a cis addition of two carbon moieties to an olefin in good to excellent yields.