Highly Enantioselective Inverse‐Electron‐Demand Hetero‐Diels–Alder Reactions Catalyzed by Modularly Designed Organocatalysts

Sinha, Debabrata; Perera, Sandun; Zhao, Caidan

doi:10.1002/chem.201300168

Cited by 68 publications

(24 citation statements)

References 58 publications

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“…A few years back we introduced modularly designed organocatalysts (MDOs), which could self‐assemble under the reaction conditions from carefully designed precatalyst modules through ionic interactions, for catalyzing organic reactions . Recently, we successfully applied MDOs in organocatalyzed domino reactions.…”

Section: Synergistic Organocatalysismentioning

confidence: 99%

Recent Progress in Organocatalytic Asymmetric Domino Transformations

2017

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Sustainability in chemical synthesis is a major aspect of the current synthetic endeavors and, therefore,m imicking the biological process in the laboratory nowadays has the highest priority.T owards achieving this goal, designingorganic reactions in domino mode rathert han the multistep synthetic pathways andu sing organocatalysisi nstead of metal catalysis have received al ot of attention due to the inherenta dvantageso ft hese processes in terms of synthetic efficiencya nd sustainability.A saresult, the field of asymmetric organocatalytic domino reactions has witnessed tremendous progress in recent years.T his review attempts to summarize the latest developments in asymmetric organocatalyzed domino reactions since 2012, with the emphasis on the catalysts andr eactionm odes.D iscussions on the reactionm echanismsa nd the applications of the developed domino reactionm ethodsi nt he synthesis of biologically active molecules and natural products are also includedwhen appropriate.

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Section: Synergistic Organocatalysismentioning

confidence: 99%

Recent Progress in Organocatalytic Asymmetric Domino Transformations

2017

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“…At the same time, Zhao and co‐workers reported self‐assembled catalysts based on proline derivatives and cinchona‐alkaloid‐derived thioureas to be highly efficient catalysts for inverse‐electron‐demand hetero‐Diels–Alder cycloaddition of electron‐deficient enones and aldehydes (Scheme ) . When l ‐proline ( 7a ) and quinidine–thiourea 8a were used as the catalyst in toluene at room temperature the reactions between enones 77 and propanal generated mixtures of the aldol products and the hetero‐Diels–Alder products 79 in ratios of about 1:4 after 3 h. Prolonging the reaction time to 5 h led to almost exclusive formation of the hetero‐Diels–Alder products 79 in 92 % yield, as mixtures of two anomers (ratio 80:20), which were oxidized with pyridinium chlorochromate (PCC) to give the dihydropyranone derivatives 80 as single trans diastereomers in 90 % ee .…”

Section: Cycloadditionsmentioning

confidence: 99%

Asymmetric Supramolecular Organocatalysis: A Complementary Upgrade to Organocatalysis

2017

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The recent past has witnessed tremendous growth in the field of asymmetric synthesis through “asymmetric supramolecular organocatalysis (ASO)”. ASO emerges from many interactions between substrates and catalysts: namely substrate–catalyst, catalyst–catalyst and substrate–substrate interactions. As a result, ASO has come to be the fourth pillar of asymmetric catalysis. This review summarizes recent advances in the high‐yielding asymmetric synthesis of chiral compounds from functionally rich substrates with the aid of combinations of two or more organocatalysts working synergistically through relatively stable pre‐transition states. ASO not only assists in product formation from highly functionalized substrates with high rate/selectivity, but also sheds some light on understanding of the fundamental aspects of the pre‐transition state structures.

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“…Zhao et al demonstrated that MDO self-assembled from proline derivatives and cinchona alkaloid derived thioureas are highly efficient catalysts for inverse-electron-demand HDA reactions [103]. They developed highly enantioselective HDA reactions of electron-deficient enones 111 and aldehydes 112 by using MDO (Scheme 20).…”

Section: Inverse-electron-demand Hetero-diels–alder Reactions Of 1-oxmentioning

confidence: 99%

“…β,γ-Unsaturated α-ketophosphonates 111 may also be applied in these reactions if a higher loading of the precatalyst modules (10 mol%) is used. The authors proposed a plausible transition state on the basis of the product 116 stereochemistry and the MDO structure [103]. They showed that the aldehyde 112 reacts with the OHIC moiety of the MDO to form an ( E) -enamine.…”

Section: Inverse-electron-demand Hetero-diels–alder Reactions Of 1-oxmentioning

confidence: 99%

Recent Advances in Inverse-Electron-Demand Hetero-Diels–Alder Reactions of 1-Oxa-1,3-Butadienes

Pałasz

2016

Top Curr Chem (Z)

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This review is an endeavor to highlight the progress in the inverse-electron-demand hetero-Diels–Alder reactions of 1-oxa-1,3-butadienes in recent years. The huge number of examples of 1-oxadienes cycloadditions found in the literature clearly demonstrates the incessant importance of this transformation in pyran ring synthesis. This type of reaction is today one of the most important methods for the synthesis of dihydropyrans which are the key building blocks in structuring of carbohydrate and other natural products. Two different modes, inter- and intramolecular, of inverse-electron-demand hetero-Diels–Alder reactions of 1-oxadienes are discussed. The domino Knoevenagel hetero-Diels–Alder reactions are also described. In recent years the use of chiral Lewis acids, chiral organocatalysts, new optically active heterodienes or dienophiles have provided enormous progress in asymmetric synthesis. Solvent-free and aqueous hetero-Diels–Alder reactions of 1-oxabutadienes were also investigated. The reactivity of reactants, selectivity of cycloadditions, and chemical stability in aqueous solutions and under physiological conditions were taken into account to show the potential application of the described reactions in bioorthogonal chemistry. New bioorthogonal ligation by click inverse-electron-demand hetero-Diels–Alder cycloaddition of in situ-generated 1-oxa-1,3-butadienes and vinyl ethers was developed. It seems that some of the hetero-Diels–Alder reactions described in this review can be applied in bioorthogonal chemistry because they are selective, non-toxic, and can function in biological conditions taking into account pH, an aqueous environment, and temperature.

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Highly Enantioselective Inverse‐Electron‐Demand Hetero‐Diels–Alder Reactions Catalyzed by Modularly Designed Organocatalysts

Cited by 68 publications

References 58 publications

Recent Progress in Organocatalytic Asymmetric Domino Transformations

Recent Progress in Organocatalytic Asymmetric Domino Transformations

Asymmetric Supramolecular Organocatalysis: A Complementary Upgrade to Organocatalysis

Recent Advances in Inverse-Electron-Demand Hetero-Diels–Alder Reactions of 1-Oxa-1,3-Butadienes

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