Transition Metal-Catalyzed [6+2] Cycloadditions of 2-Vinylcyclobutanones and Alkenes:  A New Reaction for the Synthesis of Eight-Membered Rings

Wender, Paul A.; Corrêa, Arlene G.; Sato, Yoshihiro; Sun, Robert

doi:10.1021/ja001483+

Cited by 179 publications

(87 citation statements)

References 9 publications

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“…4), an unexplored version of the Pauson- Khand [2þ2þ1] cycloaddition (1!3), and an unprecedented [4þ2þ1] cycloaddition (1!6). Consistent with these possibilities, the reaction of dienyne 7 in THF in the presence of [RhCl(CO)(PPh 3 ) 2 ], AgSbF 6 , and CO produces a mixture of cycloadducts 8, 9, and 10 (Scheme 2). In the absence of CO, only the [4þ2] cycloadduct 8 is obtained in 63 % yield (60 8C, 30 min).…”

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confidence: 78%

The Dienyl Pauson–Khand Reaction

2003

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Studies in our organometallic subgroup are aimed at the design and development of new catalytic reactions, with an emphasis on processes that, in the absence of catalysts, would be forbidden or would require harsh conditions. [1,2] These studies have thus far produced the first examples of transition-metal-catalyzed [4þ4] cycloadditions of bisdienes, [3] [4þ2] cycloadditions of dienynes (and diene allenes), [4] [5þ2] cycloadditions of vinylcyclopropanes and p systems, [5] and [6þ2] cycloadditions of vinylcyclobutanones and p systems.[6] Recently, we started to investigate whether these and other two-component [mþn] cycloadditions could be converted into multicomponent [mþnþo…þx)] processes through trapping of the organometallic intermediates with additional components. [7] These investigations have thus far led to the first metal-catalyzed, three-component [5þ2þ1] cycloaddition reactions based on trapping of an intermediate in the [5þ2] cycloaddition reaction with CO.[8] The current study was directed at determining whether intermediates in the [4þ2] cycloaddition of dienynes could be similarly trapped with CO.Outlined in Scheme 1 are three competing metal-catalyzed cycloaddition pathways available for a dienyne in the

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confidence: 78%

The Dienyl Pauson–Khand Reaction

2003

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“…Scheme 1. 69 Wender and co-workers [94] also successfully accomplished a transition metal catalyzed intramolecular [6+2] cycloaddition through a reaction of 2-vinylcyclobutanone and alkene moieties (Scheme 1.70). The addition of AgOTf was not a prerequisite for the reaction to proceed when [Rh(CO) 2 Cl] 2 was used as catalyst, but the use of the Rh-Ag bimetallic catalyst did facilitate the cycloaddition.…”

Section: [3+2] Cycloaddition Reactionsmentioning

confidence: 99%

Organic Synthesis with Bimetallic Systems

Kamijo

Yamamoto

2006

ChemInform

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“…3 The acylrhodacycle B thus generated has been utilized in [4 2] annulation reactions 4 with unsaturated compounds, giving six membered cyclic carbonyl compounds (Scheme 1). 5 10 Apart from this method, ve membered acylmetallacycles can also be generated through the reactions of transition metal carbonyl complexes with alkynes 11,12 and the C C bond cleavage of cyclobutenediones/cyclobutenones 13,14 or cyclobutanones 15,16 with transition metal complexes. However, these methods suffer from the toxicity of the transition metal carbonyl complexes used, and/or dif culty in preparing the necessary cyclobutenediones or cyclobutanones.…”

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confidence: 99%

Rhodium-Catalyzed Annulation Reactions of 2-Alkynylbenzaldehydes and 2-Vinylbenzaldehyde with Unsaturated Compounds

Tanaka

2012

J. Synth. Org. Chem. Jpn.

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2 Alkynylbenzaldehydes are attractive substrates for organic reactions, because they possess two reactive functional groups, the formyl and alkynyl groups. It is well known that cationic rhodium(I) complexes are able to activate the aldehyde C H bond through oxidative addition, and the alkyne triple bond through π complexation. In this account, I describe the rhodium(I) catalyzed [4 2] annulation reactions of 2 alkynylbenzaldehydes with unsaturated compounds which proceed via benzo fused ve membered acylrhodacycles, generated through aldehyde C H bond activation followed by intramolecular cis addition of rhodium acyl hydrides to the alkyne triple bond. Analogous [4 2] annulation reactions of 2 vinylbenzaldehyde with unsaturated compounds are also described. Furthermore, the asymmetric annulation of 2 alkynylbenzaldehydes with cyclic dicarbonyl compounds catalyzed cooperatively by rhodium(I) and silver(I) complexes is also described. This unique annulation presumably proceeds via formation of benzopyrilium intermediates after alkyne activation and subsequent ketone hydroacylation through aldehyde C H bond activation. J. Synth. Org. Chem., Jpn.

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Transition Metal-Catalyzed [6+2] Cycloadditions of 2-Vinylcyclobutanones and Alkenes: A New Reaction for the Synthesis of Eight-Membered Rings

Cited by 179 publications

References 9 publications

The Dienyl Pauson–Khand Reaction

The Dienyl Pauson–Khand Reaction

Organic Synthesis with Bimetallic Systems

Rhodium-Catalyzed Annulation Reactions of 2-Alkynylbenzaldehydes and 2-Vinylbenzaldehyde with Unsaturated Compounds

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