5101-15-5

Upstream product

• 5326-34-1 4-Bromo-3-nitrotoluene 
• 5720-05-8 4-methylphenylboronic acid 
• 53078-85-6 2-bromo-5-methylaniline 
• 29289-13-2 2-iodo-4-methylaniline 
• 13194-69-9 2-iodo-5-methylaniline 
• 624-31-7 4-tolyl iodide 
• 613-33-2 (4,4'-dimethyl-1,1'-biphenyl) 
• 53356-70-0 4,4'-dimethyl-2-nitro-1,1'-biphenyl 

Downstream Products

• 246218-24-6 4,4'-dimethyl-[1,1'-biphenyl]-2-ol 
• 53356-69-7 3,7,3',7'-tetramethyl-5-(2,4,6-triisopropyl-phenyl)-5H-5λ⁵-[5,5']spirobi(benzo[b]phosphindole) 
• 22454-21-3 5-(2-isopropyl-phenyl)-3,7,3',7'-tetramethyl-5H-5λ⁵-[5,5']spirobi(benzo[b]phosphindole) 

Relevant academic research and scientific papers

Modular Tandem Mizoroki-Heck/Reductive Heck Reactions to Construct Fluorenes from Cyclic Diaryliodoniums

Starting from cyclic diaryliodoniums and terminal alkenes, a diverse set of fluorenes is conveniently constructed. The reactions catalyzed by palladium undergo one conventional Mizoroki-Heck reaction and one reductive Heck reaction. The scope of alkenes is general, leading to 29 fluorenes which would expand the structural diversity of fluorene reservoir. (Figure presented.).

Palladium-Catalyzed [4 + 3] or [2 + 2 + 3] Annulation via C-H Activation and Subsequent Decarboxylation: Access to Heptagon-Embedded Polycyclic Aromatic Hydrocarbons

The construction of a seven-membered ring in the polycyclic aromatic hydrocarbon skeleton remains a notoriously difficult but attractive challenge. Herein a novel palladium-catalyzed [4 + 3] decarboxylative annulation of 2-iodobiphenyls with 2-(2-halophenyl)acrylic acids is reported, which provides an efficient approach for assembling various tribenzo[7]annulenes via a C-H activation and decarboxylation process. Moreover, tribenzo[7]annulenes can be also synthesized via a [2 + 2 + 3] decarboxylative annulation strategy by employing readily available 1,2-halobenzenes, phenylboronic acids, and 2-(2-halophenyl)acrylic acids.

α-Bromoacrylic Acids as C1 Insertion Units for Palladium-Catalyzed Decarboxylative Synthesis of Diverse Dibenzofulvenes

Herein α-bromoacrylic acids have been employed as C1 insertion units to achieve the palladium-catalyzed [4 + 1] annulation of 2-iodobiphenyls, which provides an efficient platform for the construction of diverse dibenzofulvenes. This protocol enables the formation of double C(aryl)-C(vinyl) bonds via a C(vinyl)-Br bond cleavage and decarboxylation. It is particularly noteworthy that the method features a broad substrate scope, and various interesting frameworks, such as bridged ring, fused (hetero)aromatic ring, and divinylbenzene, can be successfully incorporated into the products.

Atmosphere-Controlled Palladium-Catalyzed Divergent Decarboxylative Cyclization of 2-Iodobiphenyls and α-Oxocarboxylic Acids

A novel palladium-catalyzed divergent decarboxylative cyclization of 2-iodobiphenyls and α-oxocarboxylic acids utilizing the atmosphere as a controlled switch is reported. Under the protection of a nitrogen atmosphere, tribenzotropones are synthesized by a [4 + 3] decarboxylative cyclization. Employing a palladium/O2 system enables a [4 + 2] decarboxylative cyclization to assemble triphenylenes. Notably, preliminary mechanistic studies indicate that the formation of triphenylenes involves a double decarboxylation.

Pd-Catalyzed C(sp3)-H Biarylation via Transient Directing Group Strategy

Here, we describe a highly selective Pd-catalyzed C(sp3)-H biarylation of 2-methylbenzaldehydes using cyclic diaryliodonium salts as arylation reagents. The key strategy is the employment of tert-leucine as a bidentate transient directing group for the proximity-driven metalation to achieve reactivity and selectivity in C-H activation. Various functionalized biaryls bearing both aldehyde and iodine functional groups were prepared successfully, which could be further transformed into a wide range of compounds with potential applications in pharmaceutical chemistry and materials science.

Copper-Catalyzed Diphenylation of P(O)-OH Bonds with Cyclic Diaryliodonium Salts

A copper-catalyzed diphenylation of P(O)?OH bonds with cyclic diaryliodonium salts is described. Valuable 2′-iodo substituted biaryl phosphinic/phosphoric acid esters were obtained in good to excellent yields, which could be further transformed to diversified building blocks for the synthesis of bioactive compounds, pharmaceuticals and functional materials.

Cyclization of 2-Biphenylthiols to Dibenzothiophenes under PdCl2/DMSO Catalysis

A palladium-catalyzed synthesis of dibenzothiophenes from 2-biphenylthiols is described. This highly efficient reaction employs a simple PdCl2/DMSO catalytic system, in which PdCl2 is the sole metal catalyst and DMSO functions as an oxidant and solvent. This transformation has broad substrate scope and operational simplicity and proceeds in high yield. The synthetic utility was demonstrated by the facile synthesis of helical dinapthothiophene 3 and an eminent organic semiconductor DBTDT 4. Importantly, highly strained trithiasumanene 5, a buckybowl of considerable synthetic challenge, was observed under this catalytic system.

Bottom-up Construction of π-Extended Arenes by a Palladium-Catalyzed Annulative Dimerization of o-Iodobiaryl Compounds

A straightforward method was developed for construction of aromatic compounds with a triphenylene core. The method involves Pd-catalyzed annulative dimerization of o-iodobiaryl compounds by double C?I and C?H bond cleavage steps. Simple reaction conditions are needed, requiring neither a ligand nor an oxidant, and the reaction tolerates a wide range of coupling partners without compromising efficiency or scalability. Significantly, the tetrachloro-substituted synthon, 1,6,11-trichloro-4-(4-chlorophenyl)triphenylene, can be generated and used to prepare a series of fully fused, small graphene nanoribbons by a late-stage arylation with arylboronic acids and a subsequent Scholl reaction. The synthetic strategy enables bottom-up access to extended π-systems in a controlled manner.

An Annulative Synthetic Strategy for Building Triphenylene Frameworks by Multiple C?H Bond Activations

C?H activation is a versatile tool for appending aryl groups to aromatic systems. However, heavy demands on multiple catalytic cycle operations and site-selectivity have limited its use for graphene segment synthesis. A Pd-catal- yzed one-step synthesis of functionalized triphenylene frameworks is disclosed, which proceeds by 2- or 4-fold C?H arylation of unactivated benzene derivatives. A Pd2(dibenzylideneacetone)3 catalytic system, using cyclic diaryliodonium salts as π-extending agents, leads to site-selective inter- and intramolecular tandem arylation sequences. Moreover, N-substituted triphenylenes are applied to a field-effect transistor sensor for rapid, sensitive, and reversible alcohol vapor detection.

Synthesis of Fluorenes Starting from 2-Iodobiphenyls and CH2Br2 through Palladium-Catalyzed Dual C-C Bond Formation

A facile and efficient approach is developed for the synthesis of fluorene and its derivatives starting from 2-iodobiphenyls and CH2Br2. A range of fluorene derivatives can be synthesized under relatively mild conditions. The reaction proceeds via a tandem palladium-catalyzed dual C-C bond formation sequence through the key dibenzopalladacyclopentadiene intermediates, which are obtained from 2-iodobiphenyls through palladium-catalyzed C-H activation.