Gold‐Katalyse: hochfunktionalisierte Cyclopentadienderivate durch intermolekulare Cyclisierung von Inamiden und Propargylcarboxylaten

Rettenmeier, Eva; Schuster, Andreas; Rudolph, Matthias; Röminger, Frank; Gade, Christoph A.; Hashmi, A. Stephen K.

doi:10.1002/ange.201301382

Cited by 44 publications

(8 citation statements)

References 101 publications

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“…(2)] 8. Very recently, highly substituted cyclopentadienes have been obtained from ynamides and propargylic carboxylates 9. However, the asymmetric synthesis of these derivatives has not been developed.…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Synthesis of Cyclopentadienes by Gold(I)‐ Catalyzed Cyclization of 1,3‐Dien‐5‐ynes

Sanjuán¹,

García‐García²,

Fernández‐Rodríguez³

et al. 2013

Adv Synth Catal

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Abstract. An asymmetric synthesis of elusive chiral cyclopentadienes has been developed by gold(I)-catalyzed alkoxycyclization of 1,3-dien-5-ynes. The application of these substrates in completely diastereoselective DielsAlder cycloaddition reactions, which can be carried out in one pot from achiral 1,3-dien-5-ynes, allow the preparation of highly functionalized products bearing five stereogenic centers with high enantiomeric excess.

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Section: Methodsmentioning

confidence: 99%

Enantioselective Synthesis of Cyclopentadienes by Gold(I)‐ Catalyzed Cyclization of 1,3‐Dien‐5‐ynes

Sanjuán¹,

García‐García²,

Fernández‐Rodríguez³

et al. 2013

Adv Synth Catal

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“…Subsequentr ing closure and elimination of the catalyst would also deliver the same final Cp. [66] Even thought he group reported 21 different Cps, the structuralv ariety was not particu-larly expansive, hinting at certaini ntrinsic limitations of the procedure.…”

Section: Fourfold-substituted Cpsmentioning

confidence: 99%

Synthetic Routes towards Multifunctional Cyclopentadienes

Frei

2019

Chemistry A European J

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Cyclopentadiene, and more importantly its functionalized derivatives, are a cornerstone of synthetic chemistry. Nowadays, they find applications in (chiral) catalysis, as ligands for organometallic complexes with potential diagnostic and therapeutic applications, and many more. This Minireview highlights the progress that has been made in the development of flexible and robust synthetic routes towards multifunctional cyclopentadienes in the last 20 years.

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“…An interesting report along these lines was presented by the group of Hashmi and co-workers wherein an efficient route to synthetically underscored cyclopentadienes 23 from propargylic esters 21 and ynamides 22 was disclosed (Scheme 6). [21] As can be understood from the proposed mechanism, initially a 1,2-acyloxy migration affords a gold carbene species 24 which then either undergoes a cyclopropenation followed by rearrangement (cf. 25, Path A type) or involvement of an iminium type intermediate 26 which is also equivalent to a β-gold vinyl cation stabilized by amide nitrogen to furnish the product 23 (Path B).…”

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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Gold‐Katalyse: hochfunktionalisierte Cyclopentadienderivate durch intermolekulare Cyclisierung von Inamiden und Propargylcarboxylaten

Cited by 44 publications

References 101 publications

Enantioselective Synthesis of Cyclopentadienes by Gold(I)‐ Catalyzed Cyclization of 1,3‐Dien‐5‐ynes

Enantioselective Synthesis of Cyclopentadienes by Gold(I)‐ Catalyzed Cyclization of 1,3‐Dien‐5‐ynes

Synthetic Routes towards Multifunctional Cyclopentadienes

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

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