Gold(I)-Catalyzed Synthesis of Furopyrans: Insight into Hetero-Diels–Alder Reactions

Pertschi, Romain; Wagner, Patrick; Ghosh, Nayan; Gandon, Vincent; Blond, Gaëlle

doi:10.1021/acs.orglett.9b02228

Cited by 14 publications

(16 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Intermediate C undergoes protodeauration to generate the oxocine-fused indole 2 . Alternatively, elimination of gold from intermediate D may occur to provide allene 4 , which is converted to the propellane-type indoline 3 , as we reported previously . The reverse reaction of allene 4 to vinyl-gold C should be much slower than the formation of G because the reaction of 4a produced only a small amount of 2a under condition A (4%, Scheme ).…”

Section: Resultsmentioning

confidence: 82%

Gold(I)-Catalyzed Cascade Cyclization of Anilines with Diynes: Controllable Formation of Eight-Membered Ring-Fused Indoles and Propellane-Type Indolines

et al. 2020

View full text Add to dashboard Cite

Heterocycle-fused indoles or indolines are distributed widely in a variety of natural products, bioactive agents, and pharmaceuticals. Herein, we describe the development of gold-catalyzed cascade reactions of anilines with diynes to form eight-membered ring-fused indoles and propellane-type indolines, both of which proceed through an intramolecular 5-endo-dig hydroamination followed by an 8-endo-dig cycloisomerization. Controllable formation of eight-membered ring-fused indoles and propellane-type indolines was achieved through selection of the ligands and/or solvents. Protic solvents such as alcohols or IPr ligand favored the formation of eight-membered ring-fused indoles, whereas the use of Buchwald’s type ligands and/or nonpolar solvents gave propellane-type indoline predominantly. This reaction provides rapid access to two types of fused nitrogen heterocycles from simple aniline derivatives.

show abstract

Section: Resultsmentioning

confidence: 82%

Gold(I)-Catalyzed Cascade Cyclization of Anilines with Diynes: Controllable Formation of Eight-Membered Ring-Fused Indoles and Propellane-Type Indolines

et al. 2020

View full text Add to dashboard Cite

show abstract

“…These results show that the specific nucleophilicity of the heteroatoms involved, induces different reactivities of the substrates. Indeed, whereas in the case of phenol ether derivatives recently described by us, [9a–c] the process starts with the intramolecular 5‐ endo ‐dig hydroalkoxylation, the more nucleophilic anilines and thioethers counterparts attack first the gold‐activated triple bond of the butynol moiety leading respectively to an indole [8] or a benzothiophene via intramolecular 5‐ endo ‐dig carboamination or carbothiolation (Figure 2).…”

Section: Resultsmentioning

confidence: 99%

Gold(I)‐Catalyzed Carbothiolation via Rearrangement of S‐Propargyl Group: An Access to 3‐Allenyl or 3‐Indenyl Benzo[b]thiophenes

et al. 2022

Self Cite

View full text Add to dashboard Cite

A series of 3‐allenyl benzo[b]thiophenes were synthesized through a gold(I)‐catalyzed domino reaction. The process consists in a 5‐endo‐dig cyclization with C−S bond formation and consecutive S‐to‐C propargyl migration via [3,3]‐sigmatropic Claisen rearrangement. With aryl substituents on both triple bonds of the substrate, subsequent intramolecular hydroarylation on the formed allenyl system led to 3‐indenyl benzo[b]thiophenes. From a substrate bearing a 3‐butynol moiety diverse fused O‐heterocycles have been obtained via intramolecular hydroalkoxylation. A gold‐mediated 1,3‐migration involving allenyl to propargyl rearrangement is also described.

show abstract

“…To set up a reliable computational model for the reaction, 1‐Me ( Scheme 2) was used as model substrate 1 and (2‐biphenyl)‐dimethylphosphine (MeJohnPhos) as a model ligand for the cationic gold complex [49,50] . Scheme 2 shows the reaction profile for the ammoniumation reaction followed by nucleophilic substitution of the (2‐alkynyl)phenylsulfonyl azetidine 1‐Me in the presence of the gold catalyst.…”

Section: Resultsmentioning

confidence: 99%

Computational Study of Benzosultam Formation through Gold(I)‐Catalyzed Ammoniumation/Nucleophilic Substitution Reaction

Pertschi

Aguirre

Pale

et al. 2021

Helvetica Chimica Acta

Self Cite

View full text Add to dashboard Cite

The Au(I)‐catalyzed reactions of (2‐alkynyl)phenylsulfonyl azetidines bearing terminal and non‐terminal alkynes in the presence of methanol as protic nucleophile to form benzosultams derivatives were studied by density functional theory (DFT) calculations. Our study highlights that gold(I) catalyzed nucleophilic addition of the nitrogen on the alkyne is favored over the direct ring opening of the azetidine by methanol, confirming the ammonium‐based mechanism. In addition, the reverse regioselectivity observed experimentally where non‐terminal alkynes favors the formation of 6‐endo‐dig‐benzosultams while terminal alkynes favor 5‐exo‐dig products is also explored through two different scenarios. The first one embraces the classical activation of the alkyne by a single Au(I) species while the second one tackles the formation of a σ,π‐digold acetylide complex. Calculations identify both pathways as competitive although only mono Au(I) complexes can lead to final products, in good agreement with experimental observation. Further details on the importance of the presence of an excess of the protic nucleophile on the protodemetallation step and the final aminal formation is also discussed.

show abstract

Gold(I)-Catalyzed Synthesis of Furopyrans: Insight into Hetero-Diels–Alder Reactions

Cited by 14 publications

References 22 publications

Gold(I)-Catalyzed Cascade Cyclization of Anilines with Diynes: Controllable Formation of Eight-Membered Ring-Fused Indoles and Propellane-Type Indolines

Gold(I)-Catalyzed Cascade Cyclization of Anilines with Diynes: Controllable Formation of Eight-Membered Ring-Fused Indoles and Propellane-Type Indolines

Gold(I)‐Catalyzed Carbothiolation via Rearrangement of S‐Propargyl Group: An Access to 3‐Allenyl or 3‐Indenyl Benzo[b]thiophenes

Computational Study of Benzosultam Formation through Gold(I)‐Catalyzed Ammoniumation/Nucleophilic Substitution Reaction

Contact Info

Product

Resources

About