Synthesis of Polycyclic Compounds by a Cascade Cycloisomerisation/Diels–Alder Reaction

Barluenga, José; Calleja, Jonás; Mendoza, Abraham; Rodríguez, Félix; Fañanás, Francisco J.

doi:10.1002/chem.201000515

Cited by 54 publications

(30 citation statements)

References 44 publications

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“…Barluenga et al have employed the gold-catalyzed oxycyclization in enynols, to develop a cascade cycloisomerization/DielsAlder reaction. 37 Starting from different enynols 50, an interesting selectivity was observed. When homopropargylic alcohols were employed, the first step went specifically through an endocycloisomerization pathway, finally yielding fused heterocyclic systems 51.…”

Section: Scheme 10mentioning

confidence: 95%

Gold catalyzed oxycyclizations of alkynols and alkyndiols

2011

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Alkynols and alkyndiols represent excellent building blocks for oxycyclization reactions, leading to a large number of different cyclic structures in one single step. Recently, the use of gold salts and gold complexes has been introduced as an alternative to the traditional methods, providing mild reaction conditions and high group compatibility. This overview focuses on the most recent achievements on gold-catalyzed oxycyclizations, both from alkynols and alkyndiols, and their use in different cascade processes and total synthesis.

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Section: Scheme 10mentioning

confidence: 95%

Gold catalyzed oxycyclizations of alkynols and alkyndiols

2011

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“…Thus, the reaction of enynol derivatives 57 with olefins 58 (tetracyanoethylene or N-phenylmaleimide) in the presence of 3 mol% of gold(III) chloride afforded the desired products 59 in high yield and as single diastereomers (Scheme 29). 30…”

Section: Scheme 27 10 Cascade Hydroalkoxylation/diels-alder Reactionsmentioning

confidence: 99%

“…The subsequent Diels-Alder reaction of these dienes with olefins 58 leads to fused bicyclic products 61 in high yield and as single diastereomers (Scheme 30). 30…”

Section: Scheme 29mentioning

confidence: 99%

Constructing Molecular Complexity from Alkynol Derivatives: A Journey from Fischer Carbene Complexes to Tandem Catalysis with Gold and other Carbophilic Lewis Acids

Rodríguez

Fañanás

2013

Synlett

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One of the main challenges that organic chemists face is the development of new ways to obtain novel compounds in a fast, clean, and efficient manner. Among the strategies developed to achieve this goal are multicomponent and tandem reactions, which offer the opportunity of building up complex molecules from simple starting materials in a single synthetic operation. Alkynol derivatives are one example of these simple starting materials which, combined with other appropriate reagents, are easily transformed into interesting final products.The explosion of research that has occurred in recent years in the field of gold catalysis has served to further raise the value of alkynol derivatives as useful materials for multicomponent and cascade reactions. This account describes our recent work in this area and shows how simple reagents can be catalytically converted into complex molecules containing interesting motifs, such as eight-membered rings, [3.3.1]-and [3.2.1]-bicyclic compounds, quinolines, and spiroacetals. In addition, the application of the methods developed is shown in the total syntheses of some natural products, such as berkelic acid.

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“…[5] Homogeneous catalysts have the characteristics of high activity and wide molecular modification. [6] As more promising alternatives, heterogeneous catalysts, such as zeolite, metal oxides and heteropoly acids, have excellent separation capacity and reusability. [7] Generally, acid catalysts, such as Brønsted acid and Lewis acid catalysts, are used to promote cycloaddition reactions.…”

Section: Introductionmentioning

confidence: 99%

Temperature‐Dependent Diels‐Alder Cycloaddition on Polyoxometalate‐Supported Single‐Atom Catalysts M₁/PTA (M=Mn, Fe, Co, Ru, Rh, Pd, Os, Ir and Pt; PTA=[PW₁₂₄₀]³⁻)

et al. 2021

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Diels-Alder (DÀ A) reaction shaped both the art and science of total synthesis to some degree, while the effect of temperature on DÀ A activity over polyoxometalates supported single-atom catalysts (SACs) has been infrequently studied and simulated using theoretical calculations. Herein, cycloaddition of 1,3butadiene (C 4 H 6 ) and ethylene (C 2 H 4 ) was employed as a model DÀ A reaction. The multitudes of SACs M 1 /PTA (M=Mn, Fe, Co, Ru, Rh, Pd, Os, Ir and Pt; PTA=[PW 12 O 40 ] 3À ) were examined by DFT-M06l computations to understand the reaction mechanism on a molecular level. The adsorption energies of reactant and product, and activation energy barriers for all the studied SAC systems have the same variation trends with the temperature variations. Considering that the adsorption for C 4 H 6 is always stronger than that of C 2 H 4 in all the studied systems, the initial adsorption configurations is the M 1 /PTA SACs adsorbed one C 4 H 6 molecule. Three SACs, namely the Co 1 /PTA and Rh 1 /PTA at 100 K, Rh 1 /PTA at 300 K were identified, which show predominant catalytic activity and the corresponding activation energy barriers are 4.21, 8.51 and 5.11 kcal mol À 1 , respectively. The bonding interaction between adsorbate C 4 H 6 and SACs arises from the occupied molecular orbitals (MOs) with a mixture of π orbitals of C 4 H 6 and d atomic orbitals of the metal single atom. These theoretical calculations give new guidelines to develop high catalytic activity and cost-effective SACs towards the DÀ A reaction.

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Synthesis of Polycyclic Compounds by a Cascade Cycloisomerisation/Diels–Alder Reaction

Cited by 54 publications

References 44 publications

Gold catalyzed oxycyclizations of alkynols and alkyndiols

Gold catalyzed oxycyclizations of alkynols and alkyndiols

Constructing Molecular Complexity from Alkynol Derivatives: A Journey from Fischer Carbene Complexes to Tandem Catalysis with Gold and other Carbophilic Lewis Acids

Temperature‐Dependent Diels‐Alder Cycloaddition on Polyoxometalate‐Supported Single‐Atom Catalysts M₁/PTA (M=Mn, Fe, Co, Ru, Rh, Pd, Os, Ir and Pt; PTA=[PW₁₂₄₀]³⁻)

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Synthesis of Polycyclic Compounds by a Cascade Cycloisomerisation/Diels–Alder Reaction

Cited by 54 publications

References 44 publications

Gold catalyzed oxycyclizations of alkynols and alkyndiols

Gold catalyzed oxycyclizations of alkynols and alkyndiols

Constructing Molecular Complexity from Alkynol Derivatives: A Journey from Fischer Carbene Complexes to Tandem Catalysis with Gold and other Carbophilic Lewis Acids

Temperature‐Dependent Diels‐Alder Cycloaddition on Polyoxometalate‐Supported Single‐Atom Catalysts M1/PTA (M=Mn, Fe, Co, Ru, Rh, Pd, Os, Ir and Pt; PTA=[PW1240]3−)

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Temperature‐Dependent Diels‐Alder Cycloaddition on Polyoxometalate‐Supported Single‐Atom Catalysts M₁/PTA (M=Mn, Fe, Co, Ru, Rh, Pd, Os, Ir and Pt; PTA=[PW₁₂₄₀]³⁻)