An efficient Ir-catalyzed amidation of indoles with sulfonyl azides is disclosed, affording diverse C4-amidated exclusively under mild conditions. In this protocol, a variety commonly occurring functional groups such as formyl, acetyl, carboxyl, amide, and ester at the C3 position are well tolerated.

Abstract Described herein is the synthesis of stable oxonium‐doped polycyclic aromatic hydrocarbons (PAHs) by rhodium‐catalyzed C−H activation/annulations naphthalene‐type aldehydes with internal alkynes. This protocol provides four divergent reaction types, including two unexpected annulations an oxygen transposition process, which lead to diverse types phenalenyl‐fused pyrylium cations comprising a four‐, five‐, or six‐ring‐fused π‐conjugated core. The exhibit exquisite regioselectivity...

Disclosed herein is the merging of C-H activation and radical chemistry, enabling rapid access to a structurally diverse family fused carbohelicenes through fusion α-acetylnaphthalenes with alkynes under oxidative conditions. This cascade process exhibits exquisite chemoselectivity regioselectivity. The reaction pathway was analyzed by intermediate separations, control experiments, trapping, EPR, MALDI-TOF-MS, ESI-HRMS shown involve C2-H activation/radical reaction/C8-H relay.

Fabricating organic semiconducting materials into large-scale, well-organized architectures is critical for building high-performance molecular electronics. While graphene nanoribbons (GNRs) hold enormous promise various device applications, their assembly a well-structured monolayer or multilayer architecture poses substantial challenge. Here, we report the preparation of length-defined monodisperse GNRs via integrated iterative binomial synthesis (IIBS) strategy and self-assembly...

Reported herein is a rhodium(III)-catalyzed three-component annulation reaction of simple pyridines, alkynes, and 1,2-dichloroethane (DCE), affording streamlined pathway to diverse ring-fused pyridiniums. DCE not only serves as vinyl equivalent but also an in situ activating agent for pyridine C2-H activation. A cationic five-membered rhodacycle complex has been isolated proposed possible intermediate. This strategy can be extended other N-containing heteroarenes the synthesis...

An annulation cascade of arylnitriles with alkynes is disclosed to provide stable delocalized carbocations the ability specifically target lysosomes.

While enormous progress has been achieved in synthesizing atomically precise graphene nanoribbons (GNRs), the preparation of GNRs with a fully predetermined length and monomer sequence remains an unmet challenge. Here, we report fabrication method that provides access to structurally diverse monodisperse "designer" through utilization iterative synthesis strategy, which single is incorporated into oligomer chain during each chemical cycle. Surface-assisted cyclodehydrogenation subsequently...

Scalable fabrication of graphene nanoribbons with narrow band gaps has been a nontrivial challenge. Here, we have developed simple approach to access using hybrid edge structures. Bottom-up liquid-phase synthesis bent N = 6/8 armchair (AGNRs) achieved in high efficiency through copolymerization between an o-terphenyl monomer and naphthalene-based monomer, followed by Scholl oxidation. An unexpected 1,2-aryl migration discovered, which is responsible for introducing kinked structures into the...

Synthesis of sequence-defined monodisperse π-conjugated polymers with versatile backbones remains a substantial challenge. Here we report the development an integrated iterative binomial synthesis (IIBS) strategy to enable backbone engineering conjugated precisely controlled lengths and sequences as well high molecular weights. The IIBS capitalizes on use phenol surrogate for aryl bromide represents merge between protecting-group-aided (PAIS) (IBS). Long diverse irregular backbones, which...

Reported herein is an oxidative coupling reaction of α-C(sp3)-H bond amine with a benzylic C(sp3)-H through Mn or Co catalysis to provide diverse collections α-tertiary β-arylethylamines. This protocol features easily installed and removable coordinating activation group, wide scope substrates, low-cost metal catalysts, available starting materials synthetic simplicity.

It remains a challenge to achieve N,O-double annulations of primary benzamides with aryl alkynes due competitive N,N-double annulations. Herein, we employed sterically hindered 1-methylcyclohexane-1-carboxylic acid address this challenge, the double ortho-C-H activation and subsequent have been accomplished for first time. The resulting product can be further transformed into double-helical extended π-conjugated polycyclic heteroarene via Scholl oxidation, which exhibits blue emission high...

Here we present a divergent synthesis of brand-new types meso-N/O-heteroarene-fused (quinoidal) porphyrins through Rh-catalyzed β-C-H activation/annulation 5,15-dioxoporphyrins and dioxime derivatives with alkynes, in which the synthetic disconnections are difficult to access commonly used intramolecular cyclization strategy. Using O-methyl oxime as traceless oxidizing directing group, meso-N-embedded pyridine-fused anti-quinoidal porphyrin 3 pyridinium-fused cation 4 formed controllable...

Abstract Reported herein is a rhodium(III)‐catalyzed three‐component annulation reaction of simple pyridines, alkynes, and 1,2‐dichloroethane (DCE), affording streamlined pathway to diverse ring‐fused pyridiniums. DCE not only serves as vinyl equivalent but also an in situ activating agent for pyridine C2−H activation. A cationic five‐membered rhodacycle complex has been isolated proposed possible intermediate. This strategy can be extended other N‐containing heteroarenes the synthesis...

Abstract Disclosed herein is the merging of C−H activation and radical chemistry, enabling rapid access to a structurally diverse family fused carbohelicenes through fusion α‐acetylnaphthalenes with alkynes under oxidative conditions. This cascade process exhibits exquisite chemoselectivity regioselectivity. The reaction pathway was analyzed by intermediate separations, control experiments, trapping, EPR, MALDI‐TOF‐MS, ESI‐HRMS shown involve C2−H activation/radical reaction/C8−H relay.

Abstract Transition metal-catalyzed C–H activation and radical reactions are two versatile strategies to construct diverse organic skeletons. Here we show the construction of a class flavylium fluorophores via merge chemistry starting from (hetero)aryl ketones alkynes. This protocol is not only applicable aryl but also heteroaryl such as thiophene, benzothiophene benzofuran, thus leading structural diversity. Mechanism studies, including control experiments, intermediate separation,...

Fabricating organic semi-conducting materials into large-scale well-organized architectures is critical for building high performance molecular electronics. While graphene nanoribbons (GNRs) hold enormous promise various device applications, their assembly a well-structured monolayer or multilayer architecture poses substantial challenge. Here we report the preparation of length-defined monodisperse GNRs and self-assembly submicron-architectures with long-range order, uniform orientation as...

Abstract Described herein is the synthesis of stable oxonium‐doped polycyclic aromatic hydrocarbons (PAHs) by rhodium‐catalyzed C−H activation/annulations naphthalene‐type aldehydes with internal alkynes. This protocol provides four divergent reaction types, including two unexpected annulations an oxygen transposition process, which lead to diverse types phenalenyl‐fused pyrylium cations comprising a four‐, five‐, or six‐ring‐fused π‐conjugated core. The exhibit exquisite regioselectivity...

Scalable fabrication of graphene nanoribbons with narrow band gaps has been a nontrivial challenge. Here, we have developed unique approach to access by using hybrid edge structures. Bottom-up liquid-phase synthesis bent N=6/8 armchair (AGNRs) achieved in high efficiency through copolymerization between an ortho-terphenyl monomer and naphthalene-based monomer, followed Scholl oxidation. An unexpected 1,2-aryl migration discovered, which is responsible for introducing kinked structures the...

While enormous progress has been achieved in synthesizing atomically precise graphene nanoribbons (GNRs), the preparation of GNRs with fully predetermined length and monomer sequence remains an unmet challenge. Here we report a fabrication method that provides access to structurally diverse monodisperse “designer” through utilization iterative synthesis strategy, which single is incorporated into oligomer chain during each chemical cycle. Surface-assisted cyclodehydrogenation subsequently...