Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(14), P. 8478 - 8558

Published: Feb. 8, 2021

The catalyst-directed divergent synthesis, commonly termed as "divergent catalysis", has emerged a promising technique it allows chartering of structurally distinct products from common substrates simply by modulating the catalyst system. In this regard, gold complexes powerful catalysts they offer unique reactivity profiles compared to various other transition metal catalysts, primarily due their salient electronic and geometrical features. Owing tunable soft π-acidic nature, not only evolved superior contenders for catalyzing reactions alkynes, alkenes, allenes but also, more intriguingly, have been found provide reaction pathways over π-acid such Ag, Pt, Pd, Rh, Cu, In, Sc, Hg, Zn, etc. recent past witnessed renaissance in examples wherein, choosing or fine-tuning ligands, counteranions oxidation states itself, complete switch was observed. However, reviews documenting are sporadic; result, most reports kind remained scattered literature, thereby hampering further development burgeoning field. By conceptualizing idea "Divergent Gold Catalysis (DGC)", review aims consolidate all unified approach necessary pave way advancement exciting area. Based on factors governing divergence product formation, an explicit classification DGC provided. To gain fundamental understanding observed reactivities selectivities, is accompanied mechanistic insights at appropriate places.

Language: Английский

---

The interplay of carbophilic activation and Au(i)/Au(iii) catalysis: an emerging technique for 1,2-difunctionalization of C–C multiple bonds

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(18), P. 10422 - 10450

Published: Jan. 1, 2021

This review highlights a decade-long journey of Au-catalyzed 1,2-difunctionalization reactions C–C multiple bonds that have been realized due to the productive integration Au( i )/Au( iii )catalysis with unique π-activation mode gold complexes.

Language: Английский

---

Two-dimensional porous vermiculite-based nanocatalysts for synergetic catalytic therapy

Biomaterials, Journal Year: 2023, Volume and Issue: 295, P. 122031 - 122031

Published: Jan. 28, 2023

Language: Английский

---

Spiroindoles as Intermediates/Products in Transition Metal-Catalyzed Dearomatization of Indoles

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9442 - 9475

Published: July 3, 2023

Spirocyclic indole derivatives are fascinating tridimensional molecular scaffolds from both a synthetic and biological point of view. Among the many strategies developed to access these structures, transition metal catalysis has recently led impressive advances, especially relying on unique reactivity dearomatized spirocyclic intermediates. These species can indeed evolve toward or nonspirocyclic products through rearomatization-driven processes, which at same time highly challenging control but also source large structural diversity. This review highlights most prominent methods past decade that involve spirocyclization tethered functional group may be activated by metal, leading rearomatized products. The discussion is particularly focused spiroindoleninium intermediate complex mechanistic features regarding its evolution, dependent catalytic systems.

Language: Английский

---

DFT-Enabled Development of Hemilabile (P^∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3660 - 3674

Published: Feb. 5, 2024

Ligand-enabled oxidative addition of Csp2-X bonds to Au(I) centers has recently appeared as a valuable strategy for the development catalytic RedOx processes. Several cross-coupling reactions that were previously considered difficult achieve reported lately, thus expanding synthetic potential gold(I) complexes beyond traditional nucleophilic functionalization π-systems. MeDalPhos played an important role in this and, despite several studies on alternative structures, remains, so far, only general ligand such process. We report herein discovery and DFT-enabled structural optimization new family hemilabile (P∧N) ligands can promote aryl iodides gold(I). These flexible ligands, which possess common 2-methylamino heteroaromatic N-donor motif, are structurally electronically tunable, being easily accessible affordable. The corresponding shown outperform reactivity (MeDalPhos)Au(I) series alkoxy- amidoarylations alkenes. Their comparatively higher further highlighted thiotosylation iodides, challenging unreported C–S reaction could not be achieved under classical Pd(0/II) catalysis allows divergent access sulfur derivatives.

Language: Английский

---

Photosensitized Gold-Catalyzed Cross-Couplings of Aryl Bromides

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 7, 2025

Recently, ligand-promoted Au(I)/Au(III)-catalyzed cross-coupling reactions with aryl iodides have garnered considerable attention. Here, we report the first visible-light-driven gold-catalyzed cross-couplings of challenging bromides. In presence a (P, N)-gold(I) catalyst and an acridinium photocatalyst under blue LED irradiation, C-O coupling bromides carboxylic acids was achieved, soon it found that this photoinduced appliable for other C-C, C-N, C-S bond formation. Experimental computational studies suggest involves two discrete energy transfer (EnT) events: first, from photosensitizer produces excited-state gold(I) complex allows bottleneck oxidative addition to form Au(III) second, reductive elimination aryl-Au(III) regenerate Au(I). Collectively, new synergistic catalytic method developed here highlights tremendous potential photochemical gold catalysis via organogold complexes, as well its facilitate drug discovery due biocompatibility mildness reaction conditions.

Language: Английский

---

Gold-Catalyzed 1,2-Aminoarylation of Alkenes with External Amines

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(8), P. 4576 - 4582

Published: March 31, 2021

Reported herein is the gold-catalyzed 1,2-aminoarylation of alkenes that engages external amine as a coupling partner. Careful optimization studies revealed significant role concentration base to achieve highly chemoselective access aminoarylation products over potential C–N cross-coupled products. Overcoming all limitations, current strategy provided straightforward medicinally relevant 3-aminochroman, 2-aminotetrahydronaphthalene, and 2-aminoindane derivatives.

Language: Английский

---

Enantioselective C−H Functionalization Reactions under Gold Catalysis

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(20)

Published: Jan. 11, 2022

Abstract Transition metal‐catalyzed enantioselective functionalization of ubiquitous C−H bonds has proven to be promising field as it offers the construction chiral molecular complexity in a step‐ and atom‐economical manner. In recent years, gold emerged an attractive contender for catalyzing such reactions. The unique reactivities selectivities offered by catalysts have been exploited access numerous asymmetric transformations based on gold‐catalyzed processes. Herein, this review critically highlights major advances discoveries made under catalysis which is accompanied mechanistic insights at appropriate places.

Language: Английский

---

Recent advances in gold-complex and chiral organocatalyst cooperative catalysis for asymmetric alkyne functionalization

Chinese Chemical Letters, Journal Year: 2022, Volume and Issue: 33(12), P. 4969 - 4979

Published: April 23, 2022

Language: Английский

---

L‐Shaped Heterobidentate Imidazo[1,5‐a]pyridin‐3‐ylidene (N,C)‐Ligands for Oxidant‐Free Au^I/Au^III Catalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(12)

Published: Jan. 25, 2023

In the last decade, major advances have been made in homogeneous gold catalysis. However, Au

Language: Английский

---