On the Validity of Au-vinylidenes in the Gold-Catalyzed 1,2-Migratory Cycloisomerization of Skipped Propargylpyridines

Xia, Yuanzhi; Dudnik, Alexander S.; Li, Yahong; Gevorgyan, Vladimir

doi:10.1021/ol1024794

Cited by 96 publications

(29 citation statements)

References 70 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this case, a demanding electrophilic substitution must occur and should produce very efficiently the 3-aurated-4-iodo-2 H -chromene C and one equivalent of acid. Next, gold-assisted protonation at C-4 should afford D [57], an intermediate featuring a gold-carbene at C-3, that would require a subsequent and selective 1,2-iodine shift to furnish compounds 2 and regenerate the catalyst.…”

Section: Resultsmentioning

confidence: 99%

Gold(I)-catalyzed hydroarylation reaction of aryl (3-iodoprop-2-yn-1-yl) ethers: synthesis of 3-iodo-2H-chromene derivatives

Morán-Poladura¹,

Rubio²,

González³

2013

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

SummaryAn efficient entry to the preparation of elusive 4-unsubstituted-3-iodo-2H-chromenes has been accomplished as result of a catalytic cyclization. Thus, upon exposition of [(3-iodoprop-2-yn-1-yl)oxy]arenes to IPrAuNTf2 (3 mol %), in 1,4-dioxane at 100 °C, the desired heterocyclic motif is readily assembled. This process nicely tolerates a variety of functional groups and, interestingly, it is compatible with the presence of strong electron-withdrawing groups attached to the arene. The overall transformation can be termed as a new example of a migratory cycloisomerization and, formally, it involves well-blended 1,2-iodine shift and hydroarylation steps.

show abstract

Section: Resultsmentioning

confidence: 99%

Gold(I)-catalyzed hydroarylation reaction of aryl (3-iodoprop-2-yn-1-yl) ethers: synthesis of 3-iodo-2H-chromene derivatives

Morán-Poladura¹,

Rubio²,

González³

2013

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…A 1,2‐shift of the migrating group then furnished the desired indolizines 126 . Interestingly, use of an Ag catalyst instead of AuBr 3 also generated pyrrole‐fused heterocycles but without migration of G 91–94. The Liu group used a similar approach 95…”

Section: N‐nucleophilesmentioning

confidence: 99%

Homogeneous Gold‐Catalyzed Cyclization Reactions of Alkynes with N‐ and S‐Nucleophiles

et al. 2015

View full text Add to dashboard Cite

This review covers the formation of N-a nd S-containing heterocycles,i nitiated by gold-catalyzed nucleophilic attack of N-o rS-nucleophiles ontoa lkynes. These typeso fn ucleophiles have been somewhat overlooked as compared to their C-o rO-counterparts in other reviews.I nt his particularw ork, their intramolecular gold-mediated attack ontoa lkynesi sr eviewedi nd epth.I ti ss tructured in such af ashion that the reader will get ac learv iew of which substrates react in which cyclization mode. 1I ntroduction 2N-Nucleophiles 2.Scheme1.endo-a nd exo-dig cyclization modes for heteroatom attack onto Au-activated triple bonds. REVIEWSWouter Debrouwer et al. Scheme 2. Au(I)-catalyzed formationo fp yrroles from homopropargylic azidesb yana cetylenic Schmidt reaction. Scheme3.AuCl 3 -catalyzed preparation of fluorinated pyrroles.Scheme4.Pyrrole synthesis according to Aponick and Akai. REVIEWSHomogeneous Gold-Catalyzed Cyclization Reactions of Alkynes Scheme 32. Formationo fp yrroles via 5-exo-dig cyclization with acationic Au(I) catalyst.Scheme 33. Formationo fhomoallylic pyrroles via aza-Claisen rearrangement according to Gagosz. REVIEWSHomogeneous Gold-Catalyzed Cyclization Reactions of Alkynes Scheme 58. Au-catalyzed hydroamination in the total synthesis of (À)-Quinocarcin.Scheme 59. Reactionb etween o-alkynylbenzaldehydes and anilines under AuCl catalysis.Scheme60. Intramolecular hydroamination and transfer hydrogenation. REVIEWSHomogeneous Gold-Catalyzed Cyclization Reactions of Alkynes Scheme 79. Generation of ac ontact ion pair with retention of stereochemistry,a nd the unobserved sigmatropicr earrangement with inversion of stereochemistry.Scheme 80. Au(III)-catalyzed cycloisomerization with formation of dihydrothiazoles.Scheme81. Au(I)-catalyzed generation of an Au-carbene.

show abstract

“…Initially, a mechanism involving the isomerization of the alkyne to a gold-vinylidene was proposed. However, deuterium labeling experiments in combination with DFT calculations strongly suggest a reaction pathway in which a 1,2 migration of the G group takes place on a carbene intermediate 109 as shown in Scheme 47 96 .…”

Section: G Si Sn and Ge Migrationsmentioning

confidence: 99%

Gold‐Catalyzed Migrations and Ring Expansions

Merino

Fernández

Nevado

2014

Patai's Chemistry of Functional Groups

View full text Add to dashboard Cite

Gold complexes have been used to π‐activate alkynes, alkenes, and related moieties due to their strong affinity for these carbon systems. In this chapter we have summarized first, the most representative examples of gold‐catalyzed migrations occurring in propargylic systems and classified them according to the nature of the migrating group. In the second part, we have compiled the most relevant gold‐catalyzed ring expansions according to ring size. The current mechanistic understanding of these transformations is also presented.

show abstract

On the Validity of Au-vinylidenes in the Gold-Catalyzed 1,2-Migratory Cycloisomerization of Skipped Propargylpyridines

Cited by 96 publications

References 70 publications

Gold(I)-catalyzed hydroarylation reaction of aryl (3-iodoprop-2-yn-1-yl) ethers: synthesis of 3-iodo-2H-chromene derivatives

Gold(I)-catalyzed hydroarylation reaction of aryl (3-iodoprop-2-yn-1-yl) ethers: synthesis of 3-iodo-2H-chromene derivatives

Homogeneous Gold‐Catalyzed Cyclization Reactions of Alkynes with N‐ and S‐Nucleophiles

Gold‐Catalyzed Migrations and Ring Expansions

Contact Info

Product

Resources

About