Catalytic Synthesis and Cyclometalation of (4-Ferrocenylphenyl)pyridines DOI Creative Commons

Petr Harmach,

Benedikt N. Baumann,

Jiří Schulz

и другие.

Organometallics, Год журнала: 2024, Номер 43(17), С. 1929 - 1937

Опубликована: Авг. 24, 2024

Metal-catalyzed [2+2+2] cyclization reactions are powerful tools for the preparation of (hetero)aromatic compounds. However, they have rarely been applied in ferrocene chemistry. We employed Co-catalyzed 4-ferrocenylbenzonitrile with α,ω-diynes to prepare a series (4-ferrocenylphenyl)pyridines under solvothermal conditions or using microwave irradiation. The resulting pyridines, anellated by carbocyclic and heteroatom-containing rings, were reacted [(η5-C5Me5)MCl2]2/NaOAc (M = Rh Ir) produce respective cyclometalated complexes good yields. All compounds characterized spectroscopic methods (NMR ESI–MS) cyclic voltammetry, structures representative [(η5-C5Me5)MCl(FcC6H3–C5H2N(CH2)4-κ2C,N)] Ir; Fc ferrocenyl) determined single-crystal X-ray diffraction analysis. DFT calculations performed two model confirmed that initial electrochemical oxidation occurs at iron despite conjugated nature highest occupied molecular orbital is localized predominantly (η5-C5Me5)M moiety. An analysis bonding intrinsic bond orbitals quantum theory atoms molecules suggested more covalent M–X (X Cl N) bonds iridium complex than its rhodium congener. Notably, opposite trend was noted M–C bonds, which appear ionic Ir complex.

Язык: Английский

Access to Enantiopure Spiropyridines Enabled by Enantio-Relay Double [2 + 2 + 2] Cycloaddition and Kinetic Resolution [2 + 2 + 2] Cycloaddition of Alkynes and Nitriles DOI

Ligang Bai,

Yu-Qing Zheng,

Han-Nan Chen

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

The synthesis of enantiopure and structurally unique spiro-type molecules is utmost significance in catalysis, synthetic chemistry, related fields. We present here a general solution, nickel-catalyzed [2 + 2 2] cycloaddition, for accessing enantioenriched spiropyridines from readily available nitriles alkynes single step, including (1) enantio-relay double cycloaddition malononitriles with (2) kinetic resolution racemic pyridine-containing alkynes. Both strategies feature broad substrate scope exclusive regioselectivities, are scalable to multigram. Remarkably, the integrates enantio-induction by desymmetrizing dinitriles during initial catalytic cycle additional enantio-enhancement second (enantio-relay), yielding excellent enantioselectivities (>99% ee all examined examples). Furthermore, highly efficient strategy enables achievement exceptionally high without compromising yields (s > 200 most examples), overcoming challenges toward yield enantioselectivity. ability construct previously inaccessible spiro structures lays groundwork advancing spiropyridine derivatives, especially multinitrogen-containing compounds as potential ligands. Due perpendicular molecular orientation inherent rigidity architectures obtained, we anticipate significant promise presented approaches enhancing efforts catalysis.

Язык: Английский

Процитировано

1

Pd/Cu Dual Metal-Catalyzed Regioselective [2 + 2 + 2] Cycloaddition of Malononitriles with Alkynes to Densely Substituted Pyridines DOI

Xing-Zhen Wang,

Hong-Gui Huang, Wen‐Bo Liu

и другие.

Organic Letters, Год журнала: 2024, Номер 26(35), С. 7324 - 7329

Опубликована: Авг. 22, 2024

Transition metal-catalyzed [2 + 2 2] cycloaddition of nitriles and two alkynes is an efficient method for assembling pyridines. However, examples employing palladium catalysis have rarely been disclosed, the processes reactivity selectivity remain unclear. We report here a palladium/copper dual diynyl-tethered malononitriles terminal to synthesize densely substituted This features good substrate scope, synthetically useful yields, perfect regioselectivity. The derivatization pyridine products demonstrates potential application this in synthesizing heterocycles as ligands photocatalysis. Preliminary mechanistic studies suggest that reaction undergoes aza-oxidative Pd(0) with nitrile alkyne, followed by alkyne insertion reductive elimination. presence copper crucial its

Язык: Английский

Процитировано

4

Nickel-Catalyzed Reductive Alkyne Hydrocyanation Enabled by Malononitrile and a Formaldehyde Additive DOI

Anthony F. Palermo,

B Chiu,

Purvish Patel

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер unknown

Опубликована: Ноя. 4, 2023

The development of a nickel-catalyzed reductive alkyne hydrocyanation is described using 2-methyl-2-phenylmalononitrile (MPMN), C-bound electrophilic transnitrilation reagent. Reproducibility issues led to the detection oxidized hemiaminal impurities within N,N-dimethylacetamide. These release formaldehyde in situ, which was ultimately identified as critical reaction additive. A range diaryl and aryl-alkyl alkynes underwent hydrocyanation. Mechanistic experiments revealed that MPMN undergo Ni-catalyzed coupling two π-components, leading controlled glycolonitrile active cyanating agent.

Язык: Английский

Процитировано

9

Concise synthesis of succinimide-fused 1,3-cyclohexadienes via Co-catalyzed [2 + 2 + 2] cycloaddition of 1,6-diynes and maleimides DOI

Kaili Cen,

Ziyi Zhai,

Yuan Liu

и другие.

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(11), С. 3257 - 3262

Опубликована: Янв. 1, 2024

This work has realized a facile assembly of succinimide-fused 1,3-cyclohexadienes via Co-catalyzed [2 + 2 2] cycloaddition 1,6-diynes to maleimides. Furthermore, the oxidation was carried out under I /MeONa.

Язык: Английский

Процитировано

3

Theoretical Study on the Internal Conversion Decay Pathways of Bithiophene-Fused Isoquinolines DOI
Takeshi Yoshikawa,

A. Inoue,

K. Aoyama

и другие.

The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown

Опубликована: Янв. 10, 2025

In this study, the radiative and nonradiative decay pathways from first singlet excited states (denoted as S

Язык: Английский

Процитировано

0

The literature of heterocyclic chemistry, part XXII, 2022 DOI
Галина А. Газиева, Yu. B. Evdokimenkova, N. O. Soboleva

и другие.

Advances in heterocyclic chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0

Assembly of Fluoranthenes via Cobalt-Catalyzed [2 + 2 + 2] Cycloaddition of 1,6-Diynes with Alkynes DOI
Jinhui Cai,

Kaili Cen,

Jiahao Wei

и другие.

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 13, 2025

A series of polyaryl-substituted fluoranthenes is built in good to excellent yields via Earth-abundant metal-catalyzed [2 + 2+ 2] cycloaddition 1,6-diynes with alkynes developed. This method runs smoothly using a cheap catalytic system (CoI2/dppe/Zn) as the catalyst. Generally, this strategy exhibits low cost, high efficiency, atom economy, and functional group tolerance. Additionally, both terminal alkynes, especially heteroaryl-substituted acetylenes, internal alkyne, tolerate work. Furthermore, photophysical properties selected also investigated.

Язык: Английский

Процитировано

0

Access to Polysubstituted Pyrimidin-2-ones by Pd-Catalyzed [2 + 2 + 2] Cycloaddition of Alkyne-Tethered Malononitriles and Isocyanates DOI

Xing-Zhen Wang,

Xudong Hu, Wen‐Bo Liu

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 5, 2025

Transition-metal-catalyzed [2 + 2 2] cycloaddition reactions of alkynes, nitriles, and other π partners have been recognized as economic strategies to assemble aza-six-membered rings, but access pyrimidin-2-ones is not disclosed. Herein, we report a palladium-catalyzed 1,3-diyne-substituted malononitriles isocyanates for the construction polysubstituted pyrimidin-2-ones. This reaction features broad substrate scope moderate high yields. Conjugated pyrimidin-2-one acting fluorophore showcased potential fluorescent chemosensor Fe(III) detection.

Язык: Английский

Процитировано

0

Modular synthesis of polyfunctionalized axial-chiral 2-arylpyridines via cobalt-catalyzed asymmetric [2+2+2] cycloaddition of diynes and nitriles DOI
Zhenqi Wang,

Lin-Wen Wei,

Zhaoqing Wang

и другие.

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111377 - 111377

Опубликована: Май 1, 2025

Язык: Английский

Процитировано

0

Reductive Aza-Pauson-Khand Reaction of Nitriles DOI
Hong-Gui Huang,

Yu-Qing Zheng,

Dayou Zhong

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(19), С. 10463 - 10469

Опубликована: Май 2, 2023

γ-Lactams are valuable heterocycles in synthetic chemistry and drug development. Here, we report a reductive aza-Pauson-Khand reaction (aza-PKR) of an alkyne, nitrile, Co2(CO)8. A wide array bicyclic α,β-unsaturated γ-lactams containing two adjacent stereocenters, including all-carbon quaternary center, from alkyne-tethered malononitriles efficiently accessed high diastereoselectivity. Preliminary mechanistic investigations by experiments DFT calculations reveal that the undergoes aza-PKR process followed situ reduction. The reducing reagent generated water also provides practical tool for deuterium incorporation into γ-position lactams using D2O as source. This study represents new mode [2 + 2 1] cycloaddition enables direct use nitrile aza-heterocycle synthesis.

Язык: Английский

Процитировано

8