The key role of protodeauration in the gold-catalyzed reaction of 1,3-diynes with pyrrole and indole to form complex heterocycles

Papanastasiou, Ioannis; Faza, Olalla Nieto; López, Carlos Silva; Kolocouris, Antonios

doi:10.1039/c9qo01544b

Cited by 12 publications

(10 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Indeed, these gold-catalyzed [4+2] cycloaddition reactions involve a stepwise double hydroarylation pathway, with participation of the pyrrole-C2 and the indole-C3 in the first intermolecular hydroarylation of the diyne, and a 6-endo-dig cyclization in the second one. Density functional theory (DFT) calculations have recently corroborated this mechanistic proposal [29]. The synthetic utility of the process was fully demonstrated by Ohno and colleagues with the total synthesis of the naturally occurring dictyodendrins B, C, E, and F (see Figure 2), in which the central pyrrolo[2,3-c]carbazole cores were generated by intermolecular annulation of a conjugated diyne with a pyrrole derivative [30].…”

Section: Hydroarylation and Hydroalkylation Processesmentioning

confidence: 87%

Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Cadierno

2022

Catalysts

View full text Add to dashboard Cite

Metal-catalyzed hydrofunctionalization reactions of alkynes, i.e., the addition of Y–H units (Y = heteroatom or carbon) across the carbon–carbon triple bond, have attracted enormous attention for decades since they allow the straightforward and atom-economic access to a wide variety of functionalized olefins and, in its intramolecular version, to relevant heterocyclic and carbocyclic compounds. Despite conjugated 1,3-diynes being considered key building blocks in synthetic organic chemistry, this particular class of alkynes has been much less employed in hydrofunctionalization reactions when compared to terminal or internal monoynes. The presence of two C≡C bonds in conjugated 1,3-diynes adds to the classical regio- and stereocontrol issues associated with the alkyne hydrofunctionalization processes’ other problems, such as the possibility to undergo 1,2-, 3,4-, or 1,4-monoadditions as well as double addition reactions, thus increasing the number of potential products that can be formed. In this review article, metal-catalyzed hydrofunctionalization reactions of these challenging substrates are comprehensively discussed.

show abstract

Section: Hydroarylation and Hydroalkylation Processesmentioning

confidence: 87%

Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Cadierno

2022

Catalysts

View full text Add to dashboard Cite

show abstract

“…While the use of alkynes, allenes, and different non‐conjugated diynes as substrates for homogeneous gold catalysis is very popular, [1–19] alkenes and 1,3‐butadiyne derivatives have been used in only a few examples [15,20–25] . However, as shown in this work, the latter ones can be converted into 1,3‐butadiene di‐ethers by gold catalysis giving access to versatile building blocks with a wide range of applications.…”

Section: Introductionmentioning

confidence: 88%

“…So far, only a few gold-catalyzed functionalizations of 1,3-butadiynes can be found in literature and functionalizations using O-nucleophiles are, in contrast to alkyne substrates, rarely know. [22,[39][40][41][42] One of these examples is a cyclization of 1,3-butadiyne developed by Skrydstrup et al in 2010. [20] The two-fold 1,4addition of a bis-nucleophile enables the synthesis of pyrrole or furan derivatives, which are of particular interest due to their biologically activity.…”

Section: Introductionmentioning

confidence: 99%

“…Since the two-fold addition of alcohols to mono-alkynes is the common mode of reactivity observed, [43][44] this opens up a facile synthetic route to di(vinyl ethers), which are usually challenging to synthesize by gold catalysis. [45][46][47][48][49] Since the reactivity of 1,3-butadiynes in gold catalysis has only rarely been subjected mechanistically, [22,[50][51] special attention has now been paid to mechanistic details, including kinetic and computational studies.…”

Section: Introductionmentioning

confidence: 99%

“…So far, only a few gold‐catalyzed functionalizations of 1,3‐butadiynes can be found in literature and functionalizations using O‐nucleophiles are, in contrast to alkyne substrates, rarely know [22,39–42] . One of these examples is a cyclization of 1,3‐butadiyne developed by Skrydstrup et al .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Gold Catalysis: 2,3‐ or 1,4‐Addition to Butadiynes

Stein¹,

Pascher²,

Stracke³

et al. 2022

Adv Synth Catal

View full text Add to dashboard Cite

In the past, numerous impressive methodologies have been developed in homogeneous gold catalysis, typically using alkynes, allenes, or different non‐conjugated diyne systems as starting materials. While there are applications catalyzed by other transition metals, the use of 1,3‐butadiyne derivatives has been largely neglected in gold catalysis. In this work we present an efficient gold‐catalyzed method focusing on the functionalization of this specific type of diynes. The starting materials can be synthesized via simple Glaser Coupling, starting from cheap, highly variable, terminal alkynes. These homocoupling products, which are often observed as undesirable side‐products in Sonogashira reactions, can be converted into versatile 1,3‐butadiene derivatives in alcohol as a solvent and nucleophile under mild conditions. The possible field of application of the 1,3‐butadiene derivatives known from the literature is very broad and ranges from a use as transistor or OLED material to a use as an enzyme inhibitor. The approach presented here offers an attractive and highly effective way to versatile functionalized 1,3‐butadiene derivatives.

show abstract

Chiral Auxiliary Approach for Gold(I)‐Catalyzed Cyclizations

Cataffo,

Peña‐López,

Pedrazzani

et al. 2023

Angewandte Chemie

View full text Add to dashboard Cite

Two different classes of stereoselective cyclizations have been developed using a chiral auxiliary approach with commercially available [JohnPhosAu(MeCN)SbF6] as catalyst. First, a stereoselective cascade cyclization of 1,5‐enynes was achieved using the Oppolzer camphorsultam as chiral auxiliary. In this case, a one‐pot cyclization‐hydrolysis sequence was developed to directly afford enantioenriched spirocyclic ketones. Then, the stereoselective alkoxycyclization of 1,6‐enynes was mediated by an Evans‐type oxazolidinone. A reduction‐hydrolysis sequence was selected to remove the auxiliary to give enantioenriched b‐tetralones. DFT studies confirmed that the steric clash between the chiral auxiliary and alkene accounts for the experimentally observed diastereoselective cyclization through the Si face.

show abstract

The key role of protodeauration in the gold-catalyzed reaction of 1,3-diynes with pyrrole and indole to form complex heterocycles

Abstract: The mechanism of indole and carbazole formation via a formal [4 + 2] cycloaddition strategy is dominated by the protodeauration step.

Cited by 12 publications

References 39 publications

Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Gold Catalysis: 2,3‐ or 1,4‐Addition to Butadiynes

Chiral Auxiliary Approach for Gold(I)‐Catalyzed Cyclizations

Contact Info

Product

Resources

About