Divergent Outcomes of Gold(I)-Catalyzed Indole Additions to 3,3-Disubstituted Cyclopropenes

Young, Paul C.; Hadfield, Maximillian S.; Arrowsmith, Lynn; Macleod, Kristina M.; Mudd, Richard J.; Jordan‐Hore, James A.; Lee, Ai‐Lan

doi:10.1021/ol203418u

Cited by 75 publications

(21 citation statements)

References 55 publications

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“…[31] In 2016 Widenhöfer and co-workers accomplished gold-catalyzed anti-Markovnikov intermolecular hydroarylation of methylenecyclopropanes 14, providing an interesting methodology for the preparation of (cyclopropylmethyl)indoles 15 (Scheme 6). However, their use require strictly controlled reaction conditions, as reported, for example, by Lee for gold-catalyzed addition of indoles to 3,3-disubstituted cyclopropenes.…”

Section: Intermolecular Hydroarylation Of Alkenesmentioning

confidence: 99%

Gold‐Catalyzed Functionalization Reactions of Indole

Pirovano

2018

Eur J Org Chem

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This review summarizes the progress achieved in the last fifteen years by application of homogeneous gold catalysis in the field of indole functionalization. Several electrophilic species obtained through gold‐catalyzed π‐activation have in fact been found to react with the nucleophilic positions of indole, thus allowing its efficient manipulation. In order to furnish a complete and clear overview on the role of the catalyst, the review is organized from the perspective of the gold‐activated substrate that is reacting with the indole. In addition, in view of the ability of gold to catalyze tandem and cascade reactions, a separate section describes tandem/cascade protocols useful for the synthesis of complex polycyclic indole derivatives. Finally, gold catalysis has also been employed for the synthesis of indole‐based natural products. For this reason, a dedicated section collects all the work in which the key step to obtain these complex indoles is represented by a gold‐catalyzed reaction.

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Section: Intermolecular Hydroarylation Of Alkenesmentioning

confidence: 99%

Gold‐Catalyzed Functionalization Reactions of Indole

Pirovano

2018

Eur J Org Chem

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“…It has been reported that 3,3′‐BIMS can be obtained as by‐products in the reversible acid‐catalysed reaction of indoles with aldehydes, where 3‐vinyl indoles are the major products at low acid‐catalyst loading and at low temperatures . Similarly, gold‐catalysed/acid‐assisted addition of indoles to 3‐vinyl indoles also gives BIMs . In order to investigate the reversibility of the nucleophilic addition of the external indole to the cycle 2‐vinyl indole 4′ , the isolated BIM 3 ai was reacted under platinum conditions with methanol and the external indole 2 a .…”

Section: Resultsmentioning

confidence: 99%

“…More recently, new methodologies employing different metal catalysts in the reaction of indoles and unsaturated precursors have been reported . The most studied reaction is the two‐fold addition of indoles to alkynes catalysed by Au, Ga, Pd, Ru or Cu (Scheme b),– but the Au‐catalysed reaction of indoles with cyclopropenes for the synthesis of 3,3′‐BIMs has also been reported (Scheme c) . Metal‐catalysed reactions of indoles with allenes has been widely explored in recent years .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a Novel Type of 2,3′‐BIMs via Platinum‐Catalysed Reaction of Indolylallenes with Indoles

Cooper

Alonso

Eagling

et al. 2018

Chemistry A European J

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Optimisation, scope and mechanism of the platinum‐catalysed addition of indoles to indolylallenes is reported here to give 2,3′‐BIMs with a novel core structure very relevant for pharmaceutical industry. The reaction is modulated by the electronic properties of the substituents on both indoles, with the 2,3′‐BIMs favoured when electron donating groups are present. Although simple at first, a complex mechanism has been uncovered that explains the different behaviour of these systems with platinum when compared with other metals (e.g. gold). Detailed labelling studies have shown Pt‐catalysed 6‐endo‐trig cyclisation of the indollylallene as the first step of the reaction and the involvement of two cyclic vinyl‐platinum intermediates in equilibrium through a platinum carbene, as the key intermediates of the catalytic cycle towards the second nucleophilic attack and formation of the BIMs.

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“…Gold(I)‐catalyzed ring opening of 3,3‐disubstituted cyclopropenes can be used to generate electrophilic species 121 which ensure a proper reaction with indoles (Scheme ) . The intermediate adduct 122 undergoes to a deauration–protonation leading to the alkenylated derivative.…”

Section: Other Alkenylating Reactantsmentioning

confidence: 99%

Regioselective Direct C‐Alkenylation of Indoles

Petrini

2017

Chemistry A European J

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The direct introduction of alkenyl groups into the indole framework avoiding its preliminary functionalization can be carried out using different synthetic strategies. Transition-metal complexes facilitate the C-H activation of indoles or alkenes allowing an efficient Csp - Csp bond formation. The hydroindolation of alkynes catalyzed by the same metal complexes or various acidic promoters can also be pursued for the alkenylation process. Conjugate addition of electron-poor alkenes and direct condensation of carbonyl derivatives with indoles are also of interest for this purpose. The regiochemical control can be exploited using the intrinsic C-3 reactivity of the indole ring. The introduction of a suitable directing group at the nitrogen atom allows the preparation of C-2 alkenylated derivatives by transition metal catalyzed reactions. This review collects the fundamental contributions in this field reported in literature during the last fifteen years.

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Divergent Outcomes of Gold(I)-Catalyzed Indole Additions to 3,3-Disubstituted Cyclopropenes

Cited by 75 publications

References 55 publications

Gold‐Catalyzed Functionalization Reactions of Indole

Gold‐Catalyzed Functionalization Reactions of Indole

Synthesis of a Novel Type of 2,3′‐BIMs via Platinum‐Catalysed Reaction of Indolylallenes with Indoles

Regioselective Direct C‐Alkenylation of Indoles

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