The reaction of a particularly electrophilic acyclic diaminocarbene with carbon monoxide: formation of <i>β</i>- and <i>γ</i>-lactams

Wallbaum, Lars; Schulz, Tim; Bruhn, Clemens; Siemeling, Ulrich

doi:10.1515/znb-2018-0255

Cited by 3 publications

References 38 publications

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The Chemistry of Azolium‐Carboxylate Zwitterions and Related Compounds: a Survey of the Years 2009–2020

Delaude

2020

Adv Synth Catal

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This review highlights the most significant advances that were accomplished in the chemistry of azolium‐carboxylate betaines within the years 2009–2020. Whenever needed, prior, seminal achievements are also briefly recalled to help put recent developments in a broader perspective. The compounds under scrutiny are zwitterions obtained upon nucleophilic addition of N‐heterocyclic carbenes (NHCs) onto carbon dioxide. We first present an overview of the various synthetic paths that give access to these inner salts before discussing their stability. The main part of this report then summarizes the numerous applications relying on NHC ⋅ CO2 zwitterions employed either in stoichiometric or catalytic proportions in the fields of organometallic chemistry and homogeneous catalysis, organic synthesis and organocatalysis, polymer chemistry, and materials science. A particular emphasis is placed on the endeavors devoted to trap carbon dioxide and to convert this greenhouse gas into valuable chemicals via the intermediacy of NHC ⋅ CO2 zwitterions. Whenever available, mechanistic considerations that help assess the pivotal role played by these species in CO2 activation are discussed. Because of their close relationship with azolium‐carboxylate betaines, azolium hydrogencarbonate salts and azolium‐methylenecarboxylate zwitterions resulting from the addition of carbon dioxide onto N‐heterocyclic olefins (NHOs) are included in this survey, which also covers the reactivity of carbon monoxide toward NHCs and related carbene species.magnified image

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The Chemistry of Azolium‐Carboxylate Zwitterions and Related Compounds: a Survey of the Years 2009–2020

Delaude

2020

Adv Synth Catal

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Four-membered ring systems

Anaya

Sánchez

2021

Progress in Heterocyclic Chemistry

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Evaluation of benzthiazolidine-based formamidinium salts for the synthesis of penem-type β-lactams by uncatalysed carbonylation of acyclic diaminocarbenes

Jonek

Buhl

Leibold

et al. 2019

Zeitschrift Für Naturforschung B

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The reaction of [iPr2N=CHCl]Cl with 2-phenylbenzthiazolidine (Ph-BtzH) and subsequent anion metathesis afforded the formamidinium salt [(Ph-Btz)CH(NiPr2)][PF6] ([1aH][PF6]). The reaction of [1aH][PF6] with (Me3Si)2NNa in the presence of grey selenium furnished the selenourea derivative 1aSe as trapping product of the acyclic diaminocarbene 1a. In the absence of selenium, a 2H-1,4-benzothiazine derivative (2) was obtained, which is an isomer of 1a, whose formation is plausibly initiated by deprotonation of [1aH]+ not at the cationic N2CH unit, but at the neighbouring PhCH position. CO was ineffective as trapping reagent for 1a. [1aH][PF6], 1aSe and 2 have been structurally characterised by X-ray diffraction.

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The reaction of a particularly electrophilic acyclic diaminocarbene with carbon monoxide: formation of β- and γ-lactams

Abstract: The reaction of carbon monoxide with the acyclic diaminocarbene iPr2N–C–TMP (TMP=2,2,6,6-tetramethylpiperidino), generated in situ from the formamidinium salt [(iPr2N)CH(TMP)][PF6] and NaN(SiMe3)2, unexpectedly afforded a mixture of β- and γ-lactams.

Cited by 3 publications

References 38 publications

The Chemistry of Azolium‐Carboxylate Zwitterions and Related Compounds: a Survey of the Years 2009–2020

The Chemistry of Azolium‐Carboxylate Zwitterions and Related Compounds: a Survey of the Years 2009–2020

Four-membered ring systems

Evaluation of benzthiazolidine-based formamidinium salts for the synthesis of penem-type β-lactams by uncatalysed carbonylation of acyclic diaminocarbenes

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