Rh(I)-Catalyzed Decarbonylation of Diynones via C–C Activation: Orthogonal Synthesis of Conjugated Diynes

Utilization of C–C bond activation as a unique mode of reactivity for constructing C–C bonds provides new strategies for preparing important organic molecules. Development of a Rh(I)-catalyzed C–C activation of diynones to synthesize symmetrical and unsymmetrical conjugated diynes through decarbonylation is reported. This C–C cleavage strategy takes advantage of the innate reactivity of conjugated ynones without relying on any ring strain or auxiliary directing group. This alkynation method also has orthogonal properties compared to typical cross-coupling reactions

Rh(I)-Catalyzed Decarbonylation of Diynones via C–C Activation: Orthogonal Synthesis of Conjugated Diynes

Utilization of C–C bond activation as a unique mode of reactivity for constructing C–C bonds provides new strategies for preparing important organic molecules. Development of a Rh(I)-catalyzed C–C activation of diynones to synthesize symmetrical and unsymmetrical conjugated diynes through decarbonylation is reported. This C–C cleavage strategy takes advantage of the innate reactivity of conjugated ynones without relying on any ring strain or auxiliary directing group. This alkynation method also has orthogonal properties compared to typical cross-coupling reactions

Rh-Catalyzed Decarbonylation of Conjugated ynones via Carbon-Alkyne Bond Activation: Reaction Scope and Mechanistic Exploration via DFT Calculations

In this full article, detailed development of a catalytic decarbonylation of conjugated monoynones to synthesize disubstituted alkynes is described. The reaction scope and limitation has been thoroughly investigated, and a broad range of functional groups including heterocycles were compatible under the catalytic conditions. Mechanistic exploration via DFT calculations has also been executed. Through the computational study, a proposed catalytic mechanism has been carefully evaluated. These efforts are expected to serve as an important exploratory study for developing catalytic alkyne-transfer reactions via carbon-alkyne bond activation.UT AustinCPRINIGMS R01GM109054-01Welch Foundation F 1781Natural Science Foundation of China 21232001Chemistr

Access to Highly Substituted 7‑Azaindoles from 2‑Fluoropyridines via 7‑Azaindoline Intermediates

A versatile synthesis of 7-azaindoles from substituted 2-fluoropyridines is described. C3-metalation and 1,4-addition to nitroolefins provide substituted 2-fluoro-3-(2-nitroethyl)­pyridines. A facile oxidative Nef reaction/reductive amination/intramolecular S_NAr sequence furnishes 7-azaindolines. Finally, optional regioselective electrophilic C5-substitution (e.g., bromination or nitration) and subsequent in situ oxidation delivers highly functionalized 7-azaindoles in high overall efficiency