Gold‐Catalyzed Cyclisation by 1,4‐Dioxidation

Claus, Vanessa; Molinari, Lise; Büllmann, Simon M.; Thusek, Jean; Rudolph, Matthias; Röminger, Frank; Hashmi, A. Stephen K.

doi:10.1002/chem.201900996

Cited by 24 publications

(14 citation statements)

References 91 publications

(15 reference statements)

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“…Thus, elimination of pyridine motif allows the formation of gold carbene species In 2019, a cationic Au catalyzed cyclization of amidesubstituted diynes and an external nucleophile was reported by Hashmi and co-workers, leading to 1-indenones 80 and 1iminoindenones (Scheme 41). [45] The reaction involves an In the same year, the Cui and co-workers demonstrated an iterative assembly of nitrile oxides 81 and ynamides for the synthesis of isoxazoles 82 and pyrroles 83 (Scheme 42). [46] The nitrile oxides 81 a, generated in situ from 81, at first undergoes Cu(I)-free cyclization with terminal ynamides to yield isoxazoles 82.…”

Section: Combination Of O-based Nucleophiles and Gold Keteniminium Speciesmentioning

confidence: 99%

Gold‐Catalyzed Transformation of Ynamides

Shandilya

Gogoi

Dutta

et al. 2021

The Chemical Record

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Ynamide, a unique species with inherited polarization of nitrogen lone pair electron to triple bond, has been largely used for the developement of novel synthetic methods and the construction of unusual N-bearing heterocycles. The reaction versatility of ynamide on umpolung reactivity, radical reactions and asymmetric synthesis have been recently reviewed. This review provides an overall scenic view into the gold catalyzed transformation of ynamides. The ynamides reactivity towards nitrogen-transfer reagents, such as azides, nitrogen ylides, isoxazoles, and anthranils; oxygen atom-transfer reagents, like nitrones, sulfoxides, and pyridine N-oxides; and carbon nucleophiles under gold catalysis are herein uncovered. The scope as well the mechanistic insights of each reaction is also briefed.

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Section: Combination Of O-based Nucleophiles and Gold Keteniminium Speciesmentioning

confidence: 99%

Gold‐Catalyzed Transformation of Ynamides

Shandilya

Gogoi

Dutta

et al. 2021

The Chemical Record

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“…Interestingly, it has also been evident that the expected carbene-oxidation product can also be obtained via a non-carbene transfer pathway. [26,27] As a result, various research groups have performed DFT calculations in addition to experimental studies to delineate the operating mechanism.…”

Section: Reactions Of Gold Carbene With Alkyne: the Mechanistic Premisementioning

confidence: 99%

“…Although it should be noted that, the failure in trapping the latent gold‐carbene species with such carbene trap experiments are only a negative indication for [1,n]‐carbene transfer process and do not substantiate any other pathway. Interestingly, it has also been evident that the expected carbene‐oxidation product can also be obtained via a non‐carbene transfer pathway [26,27] . As a result, various research groups have performed DFT calculations in addition to experimental studies to delineate the operating mechanism.…”

Section: Reactions Of Gold Carbene With Alkyne: the Mechanistic Premisementioning

confidence: 99%

Non‐Canonical Reactivity of Gold Carbene with Alkyne: An Overview of the Mechanistic Premise

Sancheti

Patil

2021

Eur J Org Chem

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The unique nature of gold carbene and its synchronous counterpart gold‐stabilized carbocation, is mainly responsible for the non‐canonical reactivity profile that it demonstrates in comparison to any other transition metal carbene. Being an important subset to this class, reactions of gold carbene with alkyne sponsor products far more diverse than cyclopropenation as canonically expected in case of other transition metal carbenes. These gold‐catalyzed reactions have largely been proposed to follow either a [1,n]‐carbene transfer process or an alternate pathway involving a direct interception of the β‐gold vinyl cation with a nucleophile at the cationic carbon. Despite of a clear distinction in structure, bonding and energy of a vinyl gold carbene and β‐gold vinyl cation; they have been found to exhibit identical reactivities like cyclopropenation, C(sp2)–H insertion, etc. making it extremely difficult to “experimentally” investigate and validate a mechanistic pathway. It is because of lack of conclusive experimental evidence, in addition to the limited number of detailed computational studies, that multiple pathways have been proposed simultaneously to rationalize the product formation. As an effort to shed light on the mechanisms of these reactions, herein, documentation of these reactions with a focus on their mechanistic premise has been presented.

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“…[16e] Hashmi and coworkers developed synthesis of indenones from amide substituted diynes under cationic gold catalysis along with diphenyl sulfoxide [Scheme 1 (vii)]. [20] And it was reported that instead of diphenyl sulfoxide they have tested with N-oxide. However, the desired products was not achieved.…”

Section: Introductionmentioning

confidence: 99%

“…Substituted indenones were synthesized by converting 1,2‐dialkynylbenzenes by utilizing I 2 O 5 and water [Scheme 1 (vi)] [16e] . Hashmi and co‐workers developed synthesis of indenones from amide substituted diynes under cationic gold catalysis along with diphenyl sulfoxide [Scheme 1 (vii)] [20] . And it was reported that instead of diphenyl sulfoxide they have tested with N ‐oxide.…”

Section: Introductionmentioning

confidence: 99%