Gold‐Catalyzed Arylative Cope Rearrangement DOI
Bidisha Paroi, Chayanika Pegu, Manoj V. Mane

и другие.

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Май 21, 2024

Abstract Cope rearrangements have garnered significant attention owing to their ability undergo structural reorganization in stereoselective manner. While substantial advances been achieved over decades, these remained applicable exclusively parent 1,5‐hexadienes. Herein, we disclose the gold‐catalyzed arylative rearrangement of 1,6‐heptadienes via a cyclization‐induced [3,3]‐rearrangement employing ligand‐enabled gold redox catalysis. Detailed mechanistic investigations including several control experiments, cross‐over experiment, HRMS analysis, 31 P NMR and DFT studies performed underpin mechanism.

Язык: Английский

DFT-Enabled Development of Hemilabile (PN) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides DOI

Karim Muratov,

Emil Zaripov, Maxim V. Berezovski

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(6), С. 3660 - 3674

Опубликована: Фев. 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.

Язык: Английский

Процитировано

26

Consolidation of the Oxidant‐Free Au(I)/Au(III) Catalysis Enabled by the Hemilabile Ligand Strategy DOI Creative Commons
Pau Font, Hugo Valdés, Xavi Ribas

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(27)

Опубликована: Апрель 30, 2024

Abstract In this minireview we survey the challenges and strategies in gold redox catalysis. Gold's reluctance to oxidative addition reactions due its high potential limits applicability. Initial attempts overcome problem focused on use of sacrificial external oxidants stoichiometric amounts bring Au(I) compounds Au(III) reactive species. Recently, innovative approaches employing hemilabile ligands, which are capable coordinating stabilizing square‐planar intermediates, thus facilitating steps enabling oxidant‐free Notable examples include (P^N) bidendate MeDalphos ligand achieve various cross‐coupling via Au(I)/Au(III). Importantly, ligand‐enabled catalysis allows merging with π‐activation, such as oxy‐ aminoarylation alkenols alkenamines using organohalides, expanding gold‘s versatility C−C C‐heteroatom bond formations unprecedented cyclizations. Moreover, recent advancements enantioselective chiral ligands also surveyed. Strikingly, versatile bidentate (C^N) competitors have appeared recently, by designing scaffolds where phosphine groups substituted N‐heterocyclic or mesoionic carbenes. Overall, these highlight evolving landscape tremendous a broad scope transformations.

Язык: Английский

Процитировано

20

Ultrafast Au(III)-Mediated Arylation of Cysteine DOI
Evan A. Doud, James A. R. Tilden, Joseph W. Treacy

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12365 - 12374

Опубликована: Апрель 24, 2024

Through mechanistic work and rational design, we have developed the fastest organometallic abiotic Cys bioconjugation. As a result, Au(III) bioconjugation reagents enable selective labeling of moieties down to picomolar concentrations allow for rapid construction complex heterostructures from peptides, proteins, oligonucleotides. This showcases how chemistry can be interfaced with biomolecules lead range reactivities that are largely unmatched by classical organic tools.

Язык: Английский

Процитировано

19

Gold‐Catalyzed Arylative Cope Rearrangement DOI
Bidisha Paroi, Chayanika Pegu, Manoj V. Mane

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Май 21, 2024

Cope rearrangements have garnered significant attention owing to their ability undergo structural reorganization in stereoselective manner. While substantial advances been achieved over decades, these remained applicable exclusively parent 1,5-hexadienes. Herein, we disclose the gold-catalyzed arylative rearrangement of 1,6-heptadienes via a cyclization-induced [3,3]-rearrangement employing ligand-enabled gold redox catalysis. Detailed mechanistic investigations including several control experiments, cross-over experiment, HRMS analysis,

Язык: Английский

Процитировано

11

Ligand‐Enabled Gold‐Catalyzed Cyanation of Organohalides DOI Open Access
Anil Kumar, Nandita Bhattacharya, Manoj V. Mane

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(47)

Опубликована: Авг. 12, 2024

Abstract Herein, we disclose the first report on gold‐catalyzed C(sp 2 )‐CN cross‐coupling reaction by employing a ligand‐enabled Au(I)/Au(III) redox catalysis. This transformation utilizes acetone cyanohydrin as nucleophilic cyanide source to convert simple aryl and alkenyl iodides into corresponding nitriles. Combined experimental computational studies highlighted crucial role of cationic silver salts in activating stable (P,N)‐AuCN complex towards oxidative addition subsequently generate key aryl‐Au(III) complexes.

Язык: Английский

Процитировано

9

Exploring the Electronic and Steric Effects of Hemilabile (P^N) Ligands in Redox Gold Catalysis: Application to the Cross-Coupling Reaction of Aliphatic Amines with Aryl Iodides DOI

Urvashi Urvashi,

Saurabh Rai, Gaurav Shukla

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

Herein, we report 17 new (P^N) ligands for redox gold catalysis, featuring various substituents at -C4, -C5, and -C6 of the aryl ring nitrogen handle. Rate kinetics experiments revealed that electron-rich -C4 -C5 positions enhanced rate oxidative addition Au(I) with C(sp2)-Br bonds compared to electron-poor substituents. Further, an unprecedented gold-catalyzed arylation aliphatic amines using electronically rich ligand (L6) -OMe group position.

Язык: Английский

Процитировано

1

Synthesis of S-alkyl phosphorothioates/phosphorodithioates via ring-opening reaction of sulfonium salts with S8, H-phosphonates or P4S10, and alcohols DOI
Lihua Yang, Lin Chen,

Bei Li

и другие.

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(20), С. 5731 - 5740

Опубликована: Янв. 1, 2024

A simple and practical method for the synthesis of S -alkyl phosphorothioates/phosphorodithioates through three-component reaction cyclic sulfonium salts with 8 , H -phosphonates, or P 4 10 alcohols was readily developed.

Язык: Английский

Процитировано

6

Visible Light/Copper Catalysis-Enabled Arylation and Alkenylation of Phosphorothioates via Site-Selective C–H Thianthrenation DOI

Guoju Guo,

Jie Ma,

Yuzhen Dong

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 24, 2024

An efficient visible light/copper-enabled arylation and alkenylation of phosphorothioates with thianthrenium salts via a C(sp

Язык: Английский

Процитировано

6

Au(I)/Au(III)-Catalyzed Sulfonylation of Aryl Iodides for the Synthesis of Various Functionalized Aryl Sulfones DOI

Lizhu Zhang,

Wenqian Du,

Jiawen Wu

и другие.

Organic Letters, Год журнала: 2024, Номер 26(43), С. 9413 - 9418

Опубликована: Окт. 18, 2024

A gold-catalyzed sulfonylation reaction of aryl iodides with different sodium sulfinates facilitated by the ligand-enabled Au(I)/Au(III) redox catalysis was developed. In C–S coupling, a variety functionalized sulfinates, such as CF3, CHF2, CH3, and alkyl groups, can react smoothly to directly construct diversely sulfones. This offers complementary method for synthesizing sulfones electron-donating groups.

Язык: Английский

Процитировано

5

Electronic Effects of Bidentate P,N-Ligands on the Elementary Steps of Au(I)/Au(III) Reactions Relevant to Cross-Coupling Chemistry DOI Creative Commons
Joseph W. Treacy, Elaine Y. Chao, Grace E. Kunkel

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 9, 2024

Oxidant-free Au(I)/Au(III)-catalyzed cross-coupling has been recently enabled by the use of bidentate

Язык: Английский

Процитировано

5