Stereoselective insertion of cyclopropenes into Mg–Mg bonds

Rekhroukh, Feriel; Zhang, Linxing; Kong, Richard Y; White, Andrew J. P.; Crimmin, Mark R.

doi:10.1039/d2cc02931f

Cited by 2 publications

(1 citation statement)

References 30 publications

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“…Functionalization of the CC double bond has been a continuing interest in the field of organic synthesis as it represents a facile approach to high-value molecules. − It has been reported that main-group dielement compounds usually undergo 1,2-addition to the CC bond of alkene substrates. − In contrast, there is no report about the activation of alkenes with dizinc compounds so far. We thus investigate the reactions of our previously reported Zn–Zn bonded compounds [ L 2 Zn 2 ] [ L = CH 3 C(2,6- i Pr 2 C 6 H 3 N)CHC(CH 3 )(NCH 2 CH 2 PR 2 ); R = Ph ( 1a ) and i Pr ( 1b )] with a series of alkenes.…”

Section: Resultsmentioning

confidence: 99%

Reductive Dimerization of Alkenes and Allenes Enabled by Photochemically Activated Zinc–Zinc Bonded Compounds

Xu,

Wang,

Rajeshkumar

et al. 2024

J. Am. Chem. Soc.

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Metal radicals have shown versatile reactivity in modern synthetic chemistry. However, the use of zinc radicals for molecular synthesis has been barely explored. Here, we show that a transient zinc radical can be formed through photoactivation of a zinc−zinc bonded compound, which is able to mediate the selective dimerization of alkenes and allenes. Treatment of dizinc compoundswith a diverse array of aromatic alkenes under UV irradiation (365 nm) facilely afforded the head-to-head coupling products, i.e., 1,4-dizinciobutanes in high yields. In addition, arylallenes could also be selectively dimerized by the dizinc compound to give 2,5-dizincyl-functionalized 1,5-hexadienes under the same conditions. Control reactions of [L Ph 2 Zn 2 ] in the presence of UV irradiation isolated a zinc phenyl complex and a trimeric zinc phosphide complex resulting from C−P bond cleavage at the tridentate ligand. Reactions of photoactivated dizinc compounds with organic spin traps, i.e., 2,2,6,6tetramethyl-1-piperidinyloxy (TEMPO) and 2,2′-bipyridine (2,2′-bpy), successfully isolated zinc radical trapping products [LZnOTEMP] and [L Ph Zn(2,2′-bpy) •− ], respectively. The profile of alkene dimerization was elucidated by density functional theory calculations, which confirmed that a transient zinc radical [LZn•] was initially generated through homolytic Zn−Zn bond cleavage via photoactivation followed by single-electron transfer and radical dimerization. The unique selectivity of the current reaction was also studied computationally.

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Section: Resultsmentioning

confidence: 99%

Reductive Dimerization of Alkenes and Allenes Enabled by Photochemically Activated Zinc–Zinc Bonded Compounds

Xu,

Wang,

Rajeshkumar

et al. 2024

J. Am. Chem. Soc.

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

Mullins,

Yuvaraj,

Sowden

et al. 2023

Chemistry A European J

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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=XylNacnac, [HC(MeCNXyl)2]−, Xyl=2,6‐xylyl; or Priso=[(DipN)2CNPri2]−, Dip=2,6‐diisopropylphenyl). Similar double reductions of [4]dendralene (4dend) have afforded the complexes, [(LMg)2(μ‐4dend)] (L=ArNacnac, 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 [{(ArNacnac)(THF)Mg}2(μ‐4dend)] (Ar=Xyl, Mes or Dip). Reaction of myrcene (Myr) with [{(XylNacnac)Mg}2] proceeds via reductive coupling of Myr to give a previously unknown acyclic, branched C20 tetra‐olefin dianion complex [{(XylNacnac)(THF)Mg}2(μ‐Myr)2]. Preliminary reactions of [(LMg)2(μ‐DMB)] with H2 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 H2 and CO.

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Stereoselective insertion of cyclopropenes into Mg–Mg bonds

Abstract: The reaction of cyclopropenes with compounds containing Mg–Mg bonds is reported. 1,2-Dimagnesiation occurs exclusively by syn-addition to the least hindered face of the alkene forming a single diastereomeric product. DFT...

Cited by 2 publications

References 30 publications

Reductive Dimerization of Alkenes and Allenes Enabled by Photochemically Activated Zinc–Zinc Bonded Compounds

Reductive Dimerization of Alkenes and Allenes Enabled by Photochemically Activated Zinc–Zinc Bonded Compounds

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

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