Rh(I)-catalyzed Pauson-Khand-type Cycloaddition Reaction of Ene-vinylidenecyclopropanes with Carbon Monoxide (CO)

Yuan, Wei; Xiang, Dong; Shi, Min; McDowell, Patrick; Li, Guigen

doi:10.1021/ol302705z

Cited by 29 publications

(6 citation statements)

References 41 publications

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“…A highly efficient Rh(I)-catalyzed Pauson–Khand-type [2 + 2 + 1] cycloaddition of ene-VDCPs 62 with CO was achieved by our group, and the reaction generated a range of fused 6,5-ring structures in good to excellent yields (Scheme ). Initially, cyclometalation of 62 with a Rh(I) catalyst gives rhodacyclic intermediate 64 . Insertion of CO into 64 provides two regioisomers, 65 and 66 , which undergo reductive elimination to produce the corresponding cycloadducts 63 .…”

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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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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“…The Rh(I)-catalyzed [2+2+1] cycloaddition reaction of enevinylidenecyclopropanes 107 with carbon monoxide was reported by Li and co-workers (Scheme 32). 48 Only in the case of monosubstituted-allene-diene 109c, the reaction required higher temperature (60 1C) and increased CO pressure (4 atm) to afford the desired product 110c with the concomitant [4+2] cycloadduct 111c. Thus, the reaction conditions of allene-dienes were generally milder than those of allene-enes (Mukai and Li's work; 80-120 1C) due to the introduction of the conjugated double bond to the olefin part.…”

Section: Intermolecular Cyclizationmentioning

confidence: 99%

[2+2+1] Cyclization of allenes

2014

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The [2+2+1] cyclization of an alkyne, an alkene and carbon monoxide, i.e., the Pauson-Khand reaction, is one of the most powerful tools for constructing a five-membered ring. In place of the alkene or alkyne part, the use of an allene functionality has proven to make this reaction more valuable for organic synthesis. This review focuses on the origin and progress of the allenic [2+2+1] cyclocarbonylation, including the chirality transfer of the allene and its synthetic applications.

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“…While containing both an allene and a cyclopropane moiety (or a methylenecyclopropane (MCP) and an alkene moieties), VDCPs are given integrated characteristics of allene and MCP together with some special reactivities, which make them excellent resources for the study of allene and cyclopropane chemistry. The chemistry of VDCPs is significantly rich and has been extensively developed by several research groups, including Mizuno, Huang, our group and others. In this Account, we primarily focus on recent developments in gold-catalyzed transformation of VDCPs and thus bring more comprehensive understanding of gold chemistry of this unique species.…”

Section: Gold-catalyzed Tandem Reactions Of Vdcpsmentioning

confidence: 99%

Gold-Catalyzed Tandem Reactions of Methylenecyclopropanes and Vinylidenecyclopropanes

2013

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Gold catalysis is often the key step in the synthesis of natural products, and is a powerful tool for tandem or domino reaction processes. Both gold salts and complexes are among the most powerful soft Lewis acids for electrophilic activation of carbon-carbon multiple bonds toward a variety of nucleophiles. The core of these reactions relies on the interaction between gold catalysts and π-bonds of alkenes, alkynes, and allenes. Activation of functional groups by gold complexes provides a useful and important method for facilitating many different organic transformations with high atom efficiency. Although they are highly strained, methylenecyclopropanes (MCPs) and vinylidenecyclopropanes (VDCPs) are readily accessible molecules that have served as useful building blocks in organic synthesis. Because of their unique structural and electronic properties, significant developments have been made in the presence of transition metal catalysts such as nickel, rhodium, palladium, and ruthenium during the past decades. However, less attention has been paid to the gold-catalyzed chemistry of MCPs and VDCPs. In this Account, we describe gold-catalyzed chemical transformations of MCPs and VDCPs developed both in our laboratory and by other researchers. Chemists have demonstrated that MCPs and VDCPs have amphiphilic properties. When MCPs or VDCPs are activated by a gold catalyst, subsequent nucleophilic attack by other reagents or ring-opening (ring-expansion) of the cyclopropane moiety will occur. However, the C-C double bonds of MCPs and VDCPs can also serve as nucleophilic reagents while more electrophilic reagents are present and activated by gold catalyst, and then further cascade reactions take place as triggered by the release of ring strain of cyclopropane. Based on this strategy, both our group and others have found some interesting gold-catalyzed transformations in recent years. These transformations of MCPs and VDCPs can produce a variety of polycyclic and heterocyclic structures, containing different sized skeletons. Moreover, we have carried out some isotopic labeling experiments and computational studies for mechanistic investigation. These reactions always give the desired products with high level control of chemo-, regio-, and diastereoselectivities, making them highly valuable for the synthesis of natural products and to the pharmaceutical industry and medicine in general.

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Rh(I)-catalyzed Pauson-Khand-type Cycloaddition Reaction of Ene-vinylidenecyclopropanes with Carbon Monoxide (CO)

Cited by 29 publications

References 41 publications

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

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

[2+2+1] Cyclization of allenes

Gold-Catalyzed Tandem Reactions of Methylenecyclopropanes and Vinylidenecyclopropanes

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