Reductive Metallation of Dendralenes and Myrcene Using Dimagnesium(I) Compounds: A Facile Route to Unsaturated Organomagnesium Compounds.

Autor: Mullins JC; School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800, Australia., Yuvaraj K; School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800, Australia., Sowden MJ; Research School of Chemistry, Australian National University, Acton, ACT, 2601, Australia., Sherburn MS; Research School of Chemistry, Australian National University, Acton, ACT, 2601, Australia., Jones C; School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800, Australia.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Jan 26; Vol. 30 (6), pp. e202303219. Date of Electronic Publication: 2023 Dec 07.
DOI: 10.1002/chem.202303219
Abstrakt: The two-electron reduction of 2,3-dimethylbuta-1,3-diene (DMB) with β-diketiminate and guanidinate substituted dimagnesium(I) compounds has given complexes in which two bidentate amido-magnesium fragments are bridged through the π-system of the DMB dianion, viz. [(LMg) 2 (μ-DMB)] (L= Xyl Nacnac, [HC(MeCNXyl) 2 ] - , Xyl=2,6-xylyl; or Priso=[(DipN) 2 CNPr i 2 ] - , Dip=2,6-diisopropylphenyl). Similar double reductions of [4]dendralene (4dend) have afforded the complexes, [(LMg) 2 (μ-4dend)] (L= Ar Nacnac, Ar=Xyl or mesityl (Mes); or Priso) in which the 4dend dianion is π-coordinated to the bidentate amido-magnesium fragments. Treatment of several such complexes with THF leads to Z- to E-isomerization of the dendralene fragment, and formation of purely σ-bonded Mg-C interactions in the THF coordinated products [{( Ar Nacnac)(THF)Mg} 2 (μ-4dend)] (Ar=Xyl, Mes or Dip). Reaction of myrcene (Myr) with [{( Xyl Nacnac)Mg} 2 ] proceeds via reductive coupling of Myr to give a previously unknown acyclic, branched C 20 tetra-olefin dianion complex [{( Xyl Nacnac)(THF)Mg} 2 (μ-Myr) 2 ]. Preliminary reactions of [(LMg) 2 (μ-DMB)] with H 2 and/or CO yielded a series of products, including novel magnesium hydride compounds, products derived from couplings of CO with the reduced DMB fragment (viz. magnesium dimethylcyclohexadienediolates), and one magnesium cyclopropanetriolate complex from the magnesium(I) induced coupling of DMB with H 2 and CO.
(© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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