ChemInform Abstract: Efficient Preparation of the Isoindoline Framework via a Six Component, Tandem Double A<sup>3</sup>‐Coupling and [2 + 2 + 2] Cycloaddition Reaction.

Bonfield, E. Ryan; Li, Chao‐Jun

doi:10.1002/chin.200828114

Cited by 5 publications

(5 citation statements)

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“…Direct Alkynylation of Glycine Amides via CDC Reaction Catalytic Nucleophilic Additions of Terminal Alkynes Li ous formaldehyde units, and a primary amine in a single synthetic operation by using a combined copper/rhodium catalyst (eq 20). 76 …”

Section: Addition Of Terminal Alkyne To Imine Tosylimine Iminium Iomentioning

confidence: 97%

The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water

2010

Acc. Chem. Res.

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365

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One of the major research endeavors in synthetic chemistry over the past two decades is the exploration of synthetic methods that work under ambient atmosphere with benign solvents, that maximize atom utilization, and that directly transform natural resources, such as renewable biomass, from their native states into useful chemical products, thus avoiding the need for protecting groups. The nucleophilic addition of terminal alkynes to various unsaturated electrophiles is a classical (textbook) reaction in organic chemistry, allowing the formation of a C-C bond while simultaneously introducing the alkyne functionality. A prerequisite of this classical reaction is the stoichiometric generation of highly reactive metal acetylides. Over the past decade, our laboratory and others have been exploring an alternative, the catalytic and direct nucleophilic addition of terminal alkynes to unsaturated electrophiles in water. We found that various terminal alkynes can react efficiently with a wide range of such electrophiles in water (or organic solvent) in the presence of simple and readily available catalysts, such as copper, silver, gold, iron, palladium, and others. In this Account, we describe the development of these synthetic methods, focusing primarily on results from our laboratory. Our studies include the following: (i) catalytic reaction of terminal alkynes with acid chloride, (ii) catalytic addition of terminal alkynes to aldehydes and ketones, (iii) catalytic addition of alkynes to C=N bonds, and (iv) catalytic conjugate additions. Most importantly, these reactions can tolerate various functional groups and, in many cases, perform better in water than in organic solvents, clearly defying classical reactivities predicated on the relative acidities of water, alcohols, and terminal alkynes. We further discuss multicomponent and enantioselective reactions that were developed. These methods provide an alternative to the traditional requirement of separate steps in classical alkyne reactions, including the pregeneration of metal acetylides with stoichiometric, highly basic reagents and the preprotection of sensitive functional groups. Accordingly, these techniques have greatly enhanced overall synthetic efficiencies and furthered our long-term objective of developing Grignard-type reactions in water.

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Section: Addition Of Terminal Alkyne To Imine Tosylimine Iminium Iomentioning

confidence: 97%

The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water

2010

Acc. Chem. Res.

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365

100

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“…Among notable recent efforts to develop new MCRs, 1 Bonfield et al recently reported an efficient method for the preparation of the isoindoline framework via a sixcomponent, tandem double A3-coupling and [2þ2þ2]-cycloaddition reaction. 2 Brauch et al have extended MCRs to seven components by taking advantage of the different chemoselectivities of the Ugi-Mumm and the Ugi-Smiles reaction. 3 Recently, the Orru group developed a one-pot reaction of up to eight components that involves nine new bond formations and eleven points of diversity.…”

Section: ' Introductionmentioning

confidence: 99%

Cerium Ammonium Nitrate-Catalyzed Multicomponent Reaction for Efficient Synthesis of Functionalized Tetrahydropyridines

2010

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A highly atom-economic one-pot synthesis of functionalized tetrahydropyridines by a multicomponent condensation reaction of β-keto ester, two equivalents of aromatic aldehyde, and two equivalents of amine in the presence of a catalytic amount of cerium ammonium nitrate (CAN) is reported. In this way, a series of pharmacologically interesting substituted piperidine derivatives were obtained in moderate to good yields at room temperature.

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“…Tetrasubstituted isoindolines can be synthesized readily from three alkyne units, two aqueous formaldehyde units and a primary amine in a single synthetic operation via a six-component coupling by using a combined copper/rhodium catalyst (eq. (27)) [128].…”

Section: Catalytic Nucleophilic Additions Via Ch Reactionmentioning

confidence: 98%

Unorthodox chemistry for an unorthodox challenge: Exploration of new chemical reactivities for a sustainable future

2011

Sci. China Chem.

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The sustainable development of our future represents an unorthodox challenge in sciences and technologies. The exploration of unconventional chemical reactivities that could potentially result in more sustainable chemical productions with efficient utilization of resource and inherent prevention of waste will provide the foundation for the synthetic chemistry of our future. As part of this endeavor, we have explored metal-mediated reactions in water to minimize protection-deprotection and the use of organic solvents, catalytic nucleophilic additions via C-H reactions to avoid generation and use of stoichiometric organic halides and metal in water, and Cross-Dehydrogenative-Coupling (CDC) reactions to minimize overall transformation steps. green chemistry, organometallic reactions in water, aldehyde-alkyne-amine coupling, cross-dehydrogenative-coupling

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ChemInform Abstract: Efficient Preparation of the Isoindoline Framework via a Six Component, Tandem Double A³‐Coupling and [2 + 2 + 2] Cycloaddition Reaction.

Cited by 5 publications

References 1 publication

The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water

The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water

Cerium Ammonium Nitrate-Catalyzed Multicomponent Reaction for Efficient Synthesis of Functionalized Tetrahydropyridines

Unorthodox chemistry for an unorthodox challenge: Exploration of new chemical reactivities for a sustainable future

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ChemInform Abstract: Efficient Preparation of the Isoindoline Framework via a Six Component, Tandem Double A3‐Coupling and [2 + 2 + 2] Cycloaddition Reaction.

Cited by 5 publications

References 1 publication

The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water

The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water

Cerium Ammonium Nitrate-Catalyzed Multicomponent Reaction for Efficient Synthesis of Functionalized Tetrahydropyridines

Unorthodox chemistry for an unorthodox challenge: Exploration of new chemical reactivities for a sustainable future

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ChemInform Abstract: Efficient Preparation of the Isoindoline Framework via a Six Component, Tandem Double A³‐Coupling and [2 + 2 + 2] Cycloaddition Reaction.