We present the discovery in TMC-1 of allenyl acetylene, HCCCHCCH, through the observation of nineteen lines with a signal-to-noise ratio ~4-15. For this species, we derived a rotational temperature of 7±1K and a column density of 1.2±0.2×10 cm. The other well known isomer of this molecule, methyl diacetylene (CHCH), has also been observed and we derived a similar rotational temperature, T=7.0±0.3 K, and a column density for its two states ( and ) of 6.5±0.3×10 cm. Hence, allenyl acetylene and methyl diacetylene have a similar abundance. Remarkably, their abundances are close to that of vinyl acetylene (CHCHCCH). We also searched for the other isomer of CH, HCCCHCCH (1.4-Pentadiyne), but only a3σ upper limit of 2.5×10 cm to the column density can be established. These results have been compared to state-of-the-art chemical models for TMC-1, indicating the important role of these hydrocarbons in its chemistry. The rotational parameters of allenyl acetylene have been improved by fitting the existing laboratory data together with the frequencies of the transitions observed in TMC-1.
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http://dx.doi.org/10.1051/0004-6361/202140482 | DOI Listing |
Molecules
November 2024
School of Chemistry, University College Dublin, Belfield, D04 V1W8 Dublin 4, Ireland.
Alkynylallenes offer the varied reactivity patterns of two different multiple bond linkages either separately or in concert. Initially, a short overview of their syntheses, structures, rearrangement mechanisms and synthetic utility, especially when treated with transition metal reagents such as gold(I), silver(I), platinum metals or metal carbonyls, is presented. Subsequently, we focus on the particular case of 1,2-dien-5-ynes (propargylallenes), whereby the shortness of the single atom bridge, and the consequent proximity of the allenyl and alkynyl moieties, facilitates metal-mediated interactions between them.
View Article and Find Full Text PDFNat Commun
November 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, India.
Skipped dienes are among the most prevalent motifs in a vast array of natural products, medicinal compounds, and fatty acids. Herein, we disclose a straightforward one-step reductive protocol under Co/PC for the synthesis of diverse 1,4-dienes with excellent regio- and stereoselectivity. The protocol employs allenyl or allyl carbonate as π-allyl source, allowing for the direct synthesis of skipped diene with a broad range of alkynes including terminal alkynes, propargylic alcohols, and internal alkynes.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany.
A (3 + 2) annulation of allenyl- and, after rapid isomerization, propargylsilanes with internal 1-aryl-1-alkynes to form 4-methylenecyclopentenes is reported. The reaction is initiated by a silylium ion, and the catalytic cycle is subsequently maintained by the self-regeneration of the silylium-ion promoter. Unlike the well-established Danheiser annulation, where the allenylsilane serves as a , the present transformation engages the allenylsilane as a .
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan 430079, P. R. China.
A Pd-catalyzed asymmetric higher-order dipolar cycloaddition between allenyl carbonates and azadienes is achieved by exploiting novel alkylidene-π-allyl-Pd dipoles. This research provides a modular platform for the synthesis of challenging chiral endocyclic allenes bearing a medium-sized heterocyclic motif and a centrally chiral stereocenter in good yields with high enantio- and diastereoselectivities (29 examples, up to 97% yield, 97:3 er and >19:1 dr). Experimental and computational studies elucidate the possible reaction mechanism and the observed stereochemical results.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education; College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079, China.
Radical-involved arylative cross-coupling reactions have recently emerged as an attractive strategy to access valuable aryl-substituted motifs. However, there still exist several challenges such as limited scope of radical precursors/acceptors, and lack of general asymmetric catalytic systems, especially regarding the multicomponent variants. Herein, we reported a general copper-Box system for asymmetric three-component arylative radical cross-coupling of vinylarenes and 1,3-enynes, with oxime carbonates and aryl boronic acids.
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