[2+1] Cycloaddition Affording Methylene- and Vinylidenecyclopropane Derivatives: A Journey around the Reactivity of Metal-Phosphinito-Phosphinous Acid Complexes

Clavier, Hervé; Buono, Gérard

doi:10.1002/tcr.201600081

Cited by 17 publications

(6 citation statements)

References 59 publications

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“…163 In order to study the influence of electron-deficient substituents on the catalytic activity of these processes, Hoge and co-workers 164,165 and their applications in this type of reactions has recently appeared. 169 Some described complexes contain a bridging-acetato ligand between the two Pd(II) centres and the optically pure t BuPhP(O)H moiety (Scheme 54).…”

Section: Palladiummentioning

confidence: 99%

“…The [2+1] cycloaddition products of Scheme 102 are chiral and display a particular chirality called geometrical enantiomorphic isomerism (also known as geometric isomerism or cis-trans isomerism) due to the E and Z configuration of the C-C double bond. Using optically pure P-stereogenic SPOs, Buono and coworkers 166,167,169 developed the asymmetric version of the Pd-catalysed [2+1] cycloaddition between norbornadienes and alkynes (Scheme 119). Several simple chiral SPOs were employed but the most enantioselective was t BuPhP(O)H, with up to 59% ee for the reaction between norbornadiene and phenylacetylene.…”

Section: Cycloadditionsmentioning

confidence: 99%

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Coordination chemistry and catalysis with secondary phosphine oxides

Gallen

Riéra

Verdaguer

et al. 2019

Catal. Sci. Technol.

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Section: Palladiummentioning

confidence: 99%

Section: Cycloadditionsmentioning

confidence: 99%

Coordination chemistry and catalysis with secondary phosphine oxides

Gallen

Riéra

Verdaguer

et al. 2019

Catal. Sci. Technol.

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“…[11] Several reviews on catalysis have appeared [12,13,14,15] and also with focus on enantioselective catalysis. [16,17] In the present review we will focus on metal-ligand cooperation of SPOs, [18,19] in which both O and P donor atoms play a critical role; the phosphorus atom anchors the ligand to the metal and the oxygen atom is available for an active role in the catalytic process, usually as a nucleophile.…”

Section: Introductionmentioning

confidence: 99%

Secondary Phosphine Oxides: Bifunctional Ligands in Catalysis

2020

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Metal complexes of secondary phosphine oxides (SPOs) were introduced as homogeneous catalysts in the 1980s for hydroformylation and hydrogenation with platinum as the metal. As neutral species, the ligand properties resemble those of the corresponding tertiary phosphines as was shown in the coordination chemistry developed in the 1970s, but the participation of the OH in bonding and reaction mechanisms provides them with a peculiar additional function. While this was already proposed and recognized in the first publications, it took a while before this found wider appreciation. Meanwhile, SPOs have become popular ligands for homogeneous catalysts, and more recently also for catalysis based on metal nanoparticles. Here we review the relatively small number of publications that pay attention to SPOs as bifunctional ligands.

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“…Very recently, Buono and Clavier reported another efficient catalytic system for [2 + 1] cycloadditions of oxanorbornene derivatives 113 and tertiary propargyl esters 110 , and the reaction gives a variety of VDCPs 114 (Scheme ). , Furthermore, VDCPs 114 can react with a series of carboxylic acids 115 under palladium catalysis to generate oxabicyclo[3.2.1]oct-2-ene derivatives 116 .…”

Section: Transition-metal-catalyzed/mediated Transformations Of Vinyl...mentioning

confidence: 99%

Recent Advances in Transition-Metal-Catalyzed/Mediated Transformations of Vinylidenecyclopropanes

Yang

Shi

2018

Acc. Chem. Res.

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Vinylidenecyclopropanes (VDCPs), having an allene moiety connected to a highly strained cyclopropyl group, have attracted a substantial amount of attention since they are fascinating building blocks for organic synthesis. During recent years, the reactions of VDCPs in the presence of a Lewis acid or a Brønsted acid and those induced by heat or light have experienced significant advancements due to the unique structural and electronic properties of VDCPs. Transition-metal-catalyzed reactions of VDCPs were not intensely investigated until the last 5 years. Recently, significant progress has been made in transition-metal-catalyzed transformations of VDCPs, and they have emerged as a new direction for the chemistry of strained small rings, especially when new types of functionalized vinylidenecyclopropanes (FVDCPs) are used as substrates. To date, many interesting transformations have been explored using these novel VDCPs under the catalysis of transition metals, such as gold, palladium, or rhodium, and various novel and useful heterocyclic or polycyclic compounds have been generated. These new findings have enriched the chemistry of strained small carbocycles. This Account will describe the transition-metal-catalyzed transformations of VDCPs recently developed in our laboratory and by other groups. The chemistry of Au-catalyzed VDCPs has been enriched and extensively developed by our group. In this respect, a new process for generating gold carbenes from VDCPs has been disclosed. The reactivity of these new gold carbenoid species was fully investigated, and many novel reaction modes based on these new gold carbenoid species were explored, including oxidation reactions, intramolecular cyclopropanations, C(sp)-H bond functionalizations, and C-O bond cleavage reactions. Rh-catalyzed reactions of VDCPs are another key field of transition-metal-catalyzed reactions of VDCPs. In particular, rhodium-catalyzed cycloadditions, Pauson-Khand reactions, and C-H bond activations of FVDCPs have been explored in detail by our group. A new trimethylenemethane rhodium (TMM-Rh) complex generated from VDCPs was discovered and utilized as an electrophilic Rh-π-allyl precursor. Moreover, some unprecedented highly regio- and enantioselective asymmetric allylic substitutions via this novel TMM-Rh complex were developed with different kinds of nucleophiles. This Account will also summarize the recent advances in palladium-, copper-, and iron-catalyzed cycloisomerization reactions of VDCPs reported by our group and others. These reactions always afford the desired products with excellent chemo-, regio-, diastereo-, and enantioselectivities, which will make them highly valuable for the synthesis of key scaffolds in natural products and pharmaceutical molecules in the future.

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[2+1] Cycloaddition Affording Methylene- and Vinylidenecyclopropane Derivatives: A Journey around the Reactivity of Metal-Phosphinito-Phosphinous Acid Complexes

Cited by 17 publications

References 59 publications

Coordination chemistry and catalysis with secondary phosphine oxides

Coordination chemistry and catalysis with secondary phosphine oxides

Secondary Phosphine Oxides: Bifunctional Ligands in Catalysis

Recent Advances in Transition-Metal-Catalyzed/Mediated Transformations of Vinylidenecyclopropanes

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