Reactivity of Stabilized Vinyl Diazo Derivatives toward Unsaturated Hydrocarbons: Regioselective Gold‐Catalyzed Carbon–Carbon Bond Formation

2013

Adv Synth Catal

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The reaction of nitriles with alkenyldiazo compounds in the presence of gold catalysts provides functionalized pyrrole derivatives in moderate to high yields. This formal [3+2] cyclization reaction takes place with complete regioselectivity. The observed regiochemical outcome suggests the attack of the nitrile to the terminal position of the alkenylgold carbenoid (vinylogous reactivity). A broad range of nitriles (including those bearing functional groups) is compatible with this cyclization reaction.

Section: Methodsmentioning

confidence: 99%

Regioselective Synthesis of Functionalized Pyrroles via Gold(I)‐Catalyzed [3+2] Cycloaddition of Stabilized Vinyl Diazo Derivatives and Nitriles

Lonzi

2013

Adv Synth Catal

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Beilstein J. Org. Chem.

“…Under otherwise identical reaction conditions, both ZnCl 2 and [Rh 2 (OAc) 4 ] yielded exclusively cyclopropane 9 in practical yields and endo selectivity. This reaction outcome differs from the comparable reactions with vinyldiazo compounds and rhodium(II) catalysts, which preferentially undergo C–H allylic insertions [31–35].…”

Section: Resultsmentioning

confidence: 76%

“…Indeed, Lee and co-worker found that the corresponding gold-catalyzed reaction leads to ring-opened products through a facile oxy-Cope-rearrangement [28]. Moreover, these structures are also not accessible with metal–vinyl carbenes generated from vinyldiazo compounds, which led again to oxy-Cope rearranged or [4 + 3]-cycloaddition products using rhodium catalysts [14,28–30], or to a C2-allylation of furan with gold catalysts [31]. Finally, to compare the reactivity of cyclopropenes and vinyldiazo compounds, we probed the reaction of 1a with 1,4-cyclohexadiene ( 8 ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 1,2-divinylcyclopropanes by metal-catalyzed cyclopropanation of 1,3-dienes with cyclopropenes as vinyl carbene precursors

González

Fuente

González

et al. 2019

The synthesis of 1,2-divinylcyclopropanes by the reaction of cyclopropenes with 1,3-dienes is reported. The process relies on the ability of ZnCl2 or [Rh2(OAc)4] to generate metal–vinyl carbene intermediates from cyclopropenes, which effect cyclopropanation of 1,3-dienes. Most of the reactions proceeded in reasonable yields while the diastereoselectivity strongly depends on the structure of the diene. An example of an intramolecular process as well as the use of furan and 1,4-cyclohexadiene as dienes are also reported.

“…Soon afterwards our group communicated the gold‐catalyzed reaction of vinyldiazo compounds and simple olefins . Interestingly, in this process neither cyclopropanes nor products arising from an allylic C‐H insertion reaction were formed.…”

Section: Coinage Metal Catalyzed Transformations Of Vinyldiazo Compoumentioning

confidence: 99%

Recent Developments in Coinage Metal Catalyzed Transformations of Stabilized Vinyldiazo Compounds: Beyond Carbenic Pathways

González‐Pelayo

2016

The Chemical Record

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Transition metal-catalyzed transformations of vinyldiazo compounds have become a versatile tool in organic synthesis. Although several transition metals have been investigated for this purpose, this field has been mainly dominated by dirhodium catalysts. Remarkable levels of chemo-, regio-, diastereo- and enantioselectivity have been reached in some of these rhodium-catalyzed transformations. In the last few years coinage metals have also emerged as useful catalysts in transformations involving vinyldiazo compounds. In some cases, highly efficient catalyst-dependent protocols arising from divergent mechanistic pathways have been reported. In this Personal Account, we aim to showcase recent advances in metal coinage catalyzed transformations of vinyldiazoacetates, an exciting field of research to which our group has actively contributed in the last few years.