84736-47-0

Upstream product

• 110-91-8 morpholine 
• 3972-65-4 1-bromo-4-tert-butylbenzene 
• 154318-75-9 4-tert-butylphenyl triflate 
• 16963-28-3 4-t-butyl-1-(morpholin-4-yl)cyclohex-1-ene 
• 247018-51-5 4-t-butylphenyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate 
• 98-54-4 para-tert-butylphenol 
• 59970-38-6 4-tert-butylphenyl mesylate 
• 22796-14-1 1-(tert-butyl)-4-(methylsulfonyl)benzene 
• 3972-56-3 4-(tert-butyl)chlorobenzene 
• 109-02-4 4-methyl-morpholine 
• 1315568-69-4 4-(tert-butyl)-2-(trimethylsilyl)phenyl trifluoromethanesulfonate 
• 98-53-3 4-tercbutyl-cyclohexanone 
• 4783-74-8 2-(4-(tert-butyl)phenoxy)pyridine 
• 253185-03-4 tert-butylbenzene 

Downstream Products

• 905966-37-2 2-(4-(tert-butyl)phenyl)-5,5-dimethyl-1,3,2-dioxaborinane 

Relevant academic research and scientific papers

Use of polymer-supported dialkylphosphinobiphenyl ligands for palladium-catalyzed amination and Suzuki reactions

The preparations of polymer-supported dialkylphosphinobiphenyl ligands (3) are reported. A palladium catalyst based on ligand 3a is active for amination and Suzuki reactions using unactivated aryl iodides, bromides, or chlorides. Filtration of the catalyst from the reaction mixtures allows for simplified product isolation via an aqueous workup. The resin-bound catalyst can be recycled without additional palladium in both the amination and Suzuki reactions.

Electrochemical Cross-Dehydrogenative Aromatization Protocol for the Synthesis of Aromatic Amines

The introduction of amines onto aromatics without metal catalysts and chemical oxidants is synthetically challenging. Herein, we report the first example of an electrochemical cross-dehydrogenative aromatization (ECDA) reaction of saturated cyclohexanones and amines to construct anilines without additional metal catalysts and chemical oxidants. This reaction exhibits a broad scope of cyclohexanones including heterocyclic ketones, affording a variety of aromatic amines with various functionalities, and shows great potential in the synthesis of biologically active compounds.

(DiMeIHeptCl)Pd: A Low-Load Catalyst for Solvent-Free (Melt) Amination

(DiMeIHeptCl)Pd, a hyper-branched N-aryl Pd NHC catalyst, has been shown to be efficient at performing amine arylation reactions in solvent-free ("melt") conditions. The highly lipophilic environment of the alkyl chains flanking the Pd center serves as lubricant to allow the complex to navigate through the paste-like environment of these mixtures. The protocol can be used on a multi-gram scale to make a variety of aniline derivatives, including substrates containing alcohol moieties.

Amination of Aryl Halides Mediated by Electrogenerated Nickel from Sacrificial Anode

Electrochemical C(sp2)?N couplings mediated by nickel salts generated from the sacrificial anode has been described for the first time. In this approach, the sacrificial nickel anode is employed as the sole source of nickel and the process, operationally simple to set up, enables the preparation of functionalized arylamine derivatives with moderate to good yields, under mild reaction conditions and without additional ligand. A cooperative process between the two electrodes is involved in the proposed mechanism.

Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and Mechanistic Study

Herein, we report a nickel-1,2-bis(dicyclohexylphosphino)ethane (dcype) complex for the catalytic Buchwald-Hartwig amination of aryl thioethers. The protocol shows broad applicability with a variety of different functional groups tolerated under the catalytic conditions. Extensive organometallic and kinetic studies support a nickel(0)-nickel(II) pathway for this transformation and revealed the oxidative addition complex as the resting state of the catalytic cycle. All the isolated intermediates have proven to be catalytically and kinetically competent catalysts for this transformation. The fleeting transmetalation intermediate has been successfully synthesized through an alternative synthetic organometallic pathway at lower temperature, allowing for in situ NMR study of the C-N bond reductive elimination step. This study addresses key factors governing the mechanism of the nickel-catalyzed Buchwald-Hartwig amination process, thus improving the understanding of this important class of reactions.

Palladium Complexes Based on Ylide-Functionalized Phosphines (YPhos): Broadly Applicable High-Performance Precatalysts for the Amination of Aryl Halides at Room Temperature

Palladium allyl, cinnamyl, and indenyl complexes with the ylide-substituted phosphines Cy3P+?C?(R)PCy2 (with R=Me (L1) or Ph (L2)) and Cy3P+?C?(Me)PtBu2 (L3) were prepared and applied as defined precatalysts in C?N coupling reactions. The complexes are highly active in the amination of 4-chlorotoluene with a series of different amines. Higher yields were observed with the precatalysts in comparison to the in situ generated catalysts. Changes in the ligand structures allowed for improved selectivities by shutting down β-hydride elimination or diarylation reactions. Particularly, the complexes based on L2 (joYPhos) revealed to be universal precatalysts for various amines and aryl halides. Full conversions to the desired products are reached mostly within 1 h reaction time at room temperature, thus making L2 to one of the most efficient ligands in C?N coupling reactions. The applicability of the catalysts was demonstrated for aryl chlorides, bromides and iodides together with primary and secondary aryl and alkyl amines, including gram-scale applications also with low catalyst loadings of down to 0.05 mol %. Kinetic studies further demonstrated the outstanding activity of the precatalysts with TOF over 10.000 h?1.

[Pd(IPr*R)(acac)Cl]: Efficient bulky Pd-NHC catalyst for Buchwald-Hartwig C-N cross-coupling reaction

A series of bulky palladium catalysts based on N-heterocyclic carbene, (Pd(NHC)(acac)Cl: NHC = IPr*me = N,N′-bis(2,6-bis(di-p-tolylmethyl)-4-methylphenyl)-imidazol-2 -ylidene, Pd(IPr*me)(acac)Cl; NHC = IPr*ipr = N,N′-bis(2,6-bis(di-4-isopropylphenyl)-4-methylphenyl)-imidazol-2 -ylidene, Pd(IPr*ipr)(acac)Cl; and NHC = IPr*tBu = N,N′-bis(2,6-bis(di-4-(tert-butyl)phenyl)- 4-methylphenyl)- imidazol-2-ylidene, Pd(IPr*tBu)(acac)Cl; acac = acetylacetonate), have been designed and synthesized. These three new catalysts showed much better catalytic activity in the Buchwald?Hartwig arylamination coupling reaction as compare to the earlier congener (IPr*)Pd(acac)Cl (IPr* = N,N′-bis(2,6-diphenylmethyl)-4-methylphenylimidazol-2-ylidene). The highly active PdII precatalyst [Pd(IPr*me)(acac)Cl] has been fully explored by using a wide range of substrates with different electronic and steric demands of coupling partners, for which up to 99% isolated yields were obtained. Remarkably, the moderate isolated yield was obtained for the challenging coupling of the amine bearing very bulky groups.

Direct Borylation of Tertiary Anilines via C-N Bond Activation

The first successful catalytic borylation of unactivated aromatic C-N bonds of tertiary anilines without the preactivation or any directing groups is demonstrated. The reactivity of both N,N-dialkylarylamines and N-arylpyrroles were investigated systematically, and the targeted products were furnished in moderate to good yields. The DFT calculation results indicated that the catalytic cycle is furnished via a five-membered cyclic transition-state due to the steric hindrance of the Ni/NHC catalytic system.

Complementary site-selectivity in arene functionalization enabled by overcoming the ortho constraint in palladium/norbornene catalysis

Achieving site-selectivity in arene functionalization that is complementary to the site-selectivity from electrophilic aromatic substitution reactions has been a long-standing quest in organic synthesis. Palladium/norbornene cooperative catalysis potentia

Three-Component Reactions of Arynes, Amines, and Nucleophiles via a One-Pot Process

An unprecedented three-component reaction of arynes, tertiary amines, and nucleophiles has been demonstrated through ammonium salt intermediates. This protocol allows access to tertiary aniline derivatives containing the piperazine motif in good-to-excell