Metal–ligand–Lewis acid multi-cooperative catalysis: a step forward in the Conia-ene reaction

Clerc, Arnaud; Marelli, Enrico; Adet, Nicolas; Monot, Julien; Martin‐Vaca, B.; Bourissou, Didier

doi:10.1039/d0sc05036a

Cited by 9 publications

(5 citation statements)

References 70 publications

(48 reference statements)

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“…The Conia-ene reaction was enabled by a multicooperative catalytic system comprised of a [(SCS)Pd] 2 complex bearing a noninnocent indenediide-based ligand and Mg(OTf) 2 in HFIP (Scheme ). The use of HFIP as an additive allowed for the reaction to be conducted at lower temperature and avoided the formation of reaction byproducts. Importantly, other fluoroalcohols such as PFTB and TFE provided lower yields than HFIP, whereas i -PrOH provided no reaction.…”

Section: Pericyclic Reactionsmentioning

confidence: 83%

HFIP in Organic Synthesis

et al. 2022

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1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability to stabilize ionic species, transfer protons, and engage in a range of other intermolecular interactions. The use of this solvent has exponentially increased in the past decade and has become a solvent of choice in some areas, such as C–H functionalization chemistry. In this review, following a brief history of HFIP in organic synthesis and an overview of its physical properties, literature examples of organic reactions using HFIP as a solvent or an additive are presented, emphasizing the effect of solvent of each reaction.

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Section: Pericyclic Reactionsmentioning

confidence: 83%

HFIP in Organic Synthesis

et al. 2022

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“…Compound 3a is not the expected product from the Conia-ene reaction. An examination of the structure of compound 3n from its starting substrate 1n confirms a 1,3-α-hydroxymethylidene migration as depicted in eq . − The preferable formation of the enol form of species 3a is due to a conjugated diene that will be more stable than its tautomerized aldehyde form. …”

mentioning

confidence: 85%

“…Conia-ene reactions initially refer to the addition of enolizable carbons to tethered alkynes through intermediate Int-1 under thermal conditions, but the temperatures are generally above 250 °C (eq 1) (Scheme ). The efficiency of Conia-ene reactions can be significantly improved by a Lewis acid , or a base catalyst, including Ag(I), Au(I), Pt(II), Zn(II), Ni(II), Ru(II), Co(I), In(III), NaH, and KOH. Equation 2 demonstrates one example of a gold-catalyzed Conia-ene reaction that proceeds through gold−π-alkyne intermediate Int-2 rather than gold enolates .…”

mentioning

confidence: 99%

Gold-Catalyzed Addition of β-Oxo Enols at Tethered Alkynes via a Non-Conia-ene Pathway: Observation of a Formal 1,3-Hydroxymethylidene Migration

Narode

Cheng

et al. 2023

Org. Lett.

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With the relay process of Ag(I)/Au(I) catalysts, a one-pot synthesis of skeletally rearranged (1-hydroxymethylidene)indene derivatives from 2-alkynylbenzaldehydes and α-diazo esters is described. This cascade sequence involves Au(I)-catalyzed 5-endo-dig attack of highly enolizable aldehydes at the tethered alkynes, leading to carbocyclizations with a formal 1,3-hydroxymethylidene transfer. On the basis of density functional theory calculations, the mechanism likely involves formation of cyclopropylgold carbenes, followed by an appealing 1,2-cyclopropane migration.

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“…[50][51][52] In addition to improving selectivity and reactivity, these novel methods can also greatly enhance the reaction processes that would not be feasible with a single metal catalyst, enabling the synthesis of novel compounds and molecular frameworks. Synergistic catalysis has often been studied by combining a transition metal catalyst with Lewis acids, 53,54 organocatalysts (e.g., Brønsted acids, N-heterocyclic carbenes, chiral amines, and Lewis bases), [55][56][57][58][59][60][61][62][63][64][65][66][67] or Lewis acids with N-heterocyclic carbenes. [68][69][70] The use of bimetallic catalysts for cross-coupling reactions is one such alternate strategy emphasized in this review.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

Recent Applications on Dual-Catalysis for C–C and C–X Cross-Coupling Reactions

Kishore¹,

Sreenivasulu²,

Dapkekar³

et al. 2022

SynOpen

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Coupling reactions stand amid the most significant reactions in synthetic organic chemistry. Of late, these coupling strategies are being viewed as a versatile synthetic tool for a wide range of organic transformations in many sectors of chemistry, ranging from indispensable synthetic scaffolds and natural products of biological significance to novel organic materials. Further, the usage of dual-catalysis in accomplishing various interesting cross-coupling transformations is an emerging field in synthetic organic chemistry, owing to their high catalytic performance rather than the usage of a single catalyst. In recent years, synthetic organic chemists have given considerable attention to hetero-dual catalysis, wherein these catalytic systems have been employed for the construction of versatile carbon-carbon [C(sp3)–C(sp3), C(sp3)–C(sp2), C(sp2)–C(sp2), etc.] and carbon-heteroatom (C-N, C-O, C-P, C-S, etc.) bonds. Therefore, in this mini-review, we are emphasizing recently developed various cross-coupling reactions catalysed by transition-metal dual-catalysis (i.e., using palladium and copper catalysts, and by omitting the reports on photoredox/metal catalysis).

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Metal–ligand–Lewis acid multi-cooperative catalysis: a step forward in the Conia-ene reaction

Abstract: An original multi-cooperative catalytic approach was developed by combining metal-ligand cooperation and Lewis acid activation. The [(SCS)Pd]2 complex featuring a non-innocent indenediide-based ligand was found to be a very efficient...

Cited by 9 publications

References 70 publications

HFIP in Organic Synthesis

HFIP in Organic Synthesis

Gold-Catalyzed Addition of β-Oxo Enols at Tethered Alkynes via a Non-Conia-ene Pathway: Observation of a Formal 1,3-Hydroxymethylidene Migration

Recent Applications on Dual-Catalysis for C–C and C–X Cross-Coupling Reactions

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