Alkyne Cross Metathesis Reactions of Extended Scope

Fürstner, Alois; Mathes, Christian

doi:10.1021/ol0068795

Cited by 86 publications

(36 citation statements)

References 26 publications

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“…Therefore, a selection of such compounds was prepared and subjected to alkyne cross‐metathesis (ACM) reactions in the presence of complex 1 as the arguably most selective catalyst known to date 3. Although a simple alkynyl ether, ‐thio ether and sulfur‐containing ynamine failed to react under the standard conditions (Figure 4), we were pleased by the good results obtained with a moderately bulky alkynylsilane,71 ‐phosphine and ‐phosphineoxide; even a phosphine‐gold complex could be transformed by ACM with 5‐decyne without damaging the organometallic entity (Table 3). Furthermore, the reactivity of these substrates could be harnessed in an unprecedented mode: whereas ring‐closure by RCAM is well established, ring‐opening alkyne metathesis has so far been restricted to polymerization reactions 72.…”

Section: Resultsmentioning

confidence: 86%

Increasing the Structural Span of Alkyne Metathesis

Persich

Llaveria

Lhermet

et al. 2013

Chemistry A European J

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103

116

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A new generation of alkyne metathesis catalysts, which are distinguished by high activity and an exquisite functional group tolerance, allows the scope of this transformation to be extended beyond its traditional range. They accept substrates that were previously found problematic or unreactive, such as propargyl alcohol derivatives, electron-deficient and electron-rich acetylenes of various types, and even terminal alkynes. Moreover, post-metathetic transformations other than semi-reduction increase the structural portfolio, as witnessed by the synthesis of a annulated phenol derivative via ring-closing alkyne metathesis (RCAM) followed by a transannular gold-catalyzed Conia-ene reaction. Further examples encompass a post-metathetic transannular ketone-alkyne cyclization with formation of a trisubstituted furan, a ruthenium-catalyzed redox isomerization, and a Meyer-Schuster rearrangement/oxa-Michael cascade. These reaction modes fueled model studies toward salicylate macrolides, furanocembranolides, and the cytotoxic macrolides acutiphycin and enigmazole A; moreover, they served as the key design elements of concise total syntheses of dehydrocurvularin (27) and the antibiotic agent A26771B (36).

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Section: Resultsmentioning

confidence: 86%

Increasing the Structural Span of Alkyne Metathesis

Persich

Llaveria

Lhermet

et al. 2013

Chemistry A European J

Self Cite

103

116

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“…30 It should be noted that TMS-protected alkynes exhibit reduced reactivity compared to typical internal alkynes. 31 …”

Section: Resultsmentioning

confidence: 99%

Multicolor Live-Cell Chemical Imaging by Isotopically Edited Alkyne Vibrational Palette

et al. 2014

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Vibrational imaging such as Raman microscopy is a powerful technique for visualizing a variety of molecules in live cells and tissues with chemical contrast. Going beyond the conventional label-free modality, recent advance of coupling alkyne vibrational tags with stimulated Raman scattering microscopy paves the way for imaging a wide spectrum of alkyne-labeled small biomolecules with superb sensitivity, specificity, resolution, biocompatibility, and minimal perturbation. Unfortunately, the currently available alkyne tag only processes a single vibrational “color”, which prohibits multiplex chemical imaging of small molecules in a way that is being routinely practiced in fluorescence microscopy. Herein we develop a three-color vibrational palette of alkyne tags using a 13C-based isotopic editing strategy. We first synthesized 13C isotopologues of EdU, a DNA metabolic reporter, by using the newly developed alkyne cross-metathesis reaction. Consistent with theoretical predictions, the mono-13C (13C≡12C) and bis-13C (13C≡13C) labeled alkyne isotopologues display Raman peaks that are red-shifted and spectrally resolved from the originally unlabeled (12C≡12C) alkynyl probe. We further demonstrated three-color chemical imaging of nascent DNA, RNA, and newly uptaken fatty-acid in live mammalian cells with a simultaneous treatment of three different isotopically edited alkynyl metabolic reporters. The alkyne vibrational palette presented here thus opens up multicolor imaging of small biomolecules, enlightening a new dimension of chemical imaging.

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“…For alkyne metathesis, there are only a few reports of synthetically useful cross-metathesis reactions [55,109] and there has been no useful model, which can predict the product selectivity. During the investigation of our molybdenum-based catalyst, we found that the tert-butyl-substituted alkyne 122 cannot homodimerize; instead, cross-metathesis between 122 and 3-hexyne was observed (Scheme 37).…”

Section: Cross-metathesismentioning

confidence: 99%

Alkyne Metathesis: Catalysts and Synthetic Applications

2007

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There has been rapid progress and growing interest in alkyne metathesis within the past decade. The availability of highly active catalysts as well as their applications in both organic synthesis and polymer chemistry has served to motivate the advancement of this field. In this article, the development of several different metathesis catalysts, including two heterogeneous ones, are reviewed with an emphasis on comparing strengths and weaknesses. In Section 4, the applications of alkyne metathesis to synthesis of natural products, conjugated polymers as well as shape-persistent macrocycles are discussed. In the last section, a comparison of alkyne metathesis to the well established alkene metathesis is given. Developing an alkyne metathesis catalyst with both high reactivity and robustness to air and moisture remains an unsolved problem of this important and useful reaction.

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Alkyne Cross Metathesis Reactions of Extended Scope

Cited by 86 publications

References 26 publications

Increasing the Structural Span of Alkyne Metathesis

Increasing the Structural Span of Alkyne Metathesis

Multicolor Live-Cell Chemical Imaging by Isotopically Edited Alkyne Vibrational Palette

Alkyne Metathesis: Catalysts and Synthetic Applications

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