Transition Metal Chemistry of Cyclopropenes and Cyclopropanes

Rubin, Michael; Rubina, Marina; Gevorgyan, Vladimir

doi:10.1021/cr050988l

Cited by 1,159 publications

(366 citation statements)

References 452 publications

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“…Methyl(4-methylphenyl)diazoacetate (Me-MPDA), 40 3,3-diphenylcyclopropene (DPCP), 18,41 R-diazoacetophenone, 42 dimethyl diazomalonate, 43 and PhCHdN 2 44 were prepared according to literature procedures. Routine 1 H and 13 C NMR spectra were recorded on a Varian VXR-400 or Bruker DRX-400 spectrometer. Mass spectra were measured on a Finnigan TSQ 700 spectrometer.…”

Section: Methodsmentioning

confidence: 99%

“…Another approach to the creation of carbene ligands in transition metal complexes is the reaction (eq 1) of 3,3-diphenylcyclopropene (DPCP) with unsaturated metal complexes (L x M). 13 Perhaps the most notable use of this reaction 20 and Re 21 have been prepared using DPCP. If DPCP were to form vinyl carbene groups on a gold metal surface, one would expect them to couple with each other to give triene products and/or to react with olefins to give vinyl cyclopropanes.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Reactions of Carbene Precursors on Bulk Gold Metal

et al. 2009

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Bulk gold metal powder, consisting of particles (5−50 μm) much larger than nanoparticles, catalyzes the coupling of carbenes generated from diazoalkanes (R2C═N2) and 3,3-diphenylcyclopropene (DPCP) to form olefins. It also catalyzes cyclopropanation reactions of these carbene precursors with styrenes. The catalytic activity of the gold powder depends on the nature of the gold particles, as determined by TEM and SEM studies. The reactions can be understood in terms of mechanisms that involve the generation of carbene R2C: intermediates adsorbed on the gold surface. Disciplines Chemistry CommentsReprinted (adapted) Abstract: Bulk gold metal powder, consisting of particles (5-50 µm) much larger than nanoparticles, catalyzes the coupling of carbenes generated from diazoalkanes (R 2 CdN 2 ) and 3,3-diphenylcyclopropene (DPCP) to form olefins. It also catalyzes cyclopropanation reactions of these carbene precursors with styrenes. The catalytic activity of the gold powder depends on the nature of the gold particles, as determined by TEM and SEM studies. The reactions can be understood in terms of mechanisms that involve the generation of carbene R 2 C: intermediates adsorbed on the gold surface.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Catalytic Reactions of Carbene Precursors on Bulk Gold Metal

et al. 2009

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“…[5] Therefore, as the most promising alternative, the catalytic versions of this transformation can be used which usually proceed under relatively mild reaction conditions. [6] Independently of the method applied, there is a problem of chemo-, regio-, and stereoselectivity of the cyclopropane-to-propene isomerization. Firstly, when the cyclopropane incorporates a side chain with reactive functional group(s), the reaction chemoselectivity is often low, since the three-membered ring opening is accompanied by the interaction of cyclopropane atom(s) with this functional group, instead of the transformation of cyclopropane into propene.…”

mentioning

confidence: 99%

Lewis Acid‐Catalyzed Isomerization of 2‐Arylcyclopropane‐1,1‐dicarboxylates: A New Efficient Route to 2‐Styrylmalonates

et al. 2010

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“…The use of Ph 3 PAuNTf 2 catalyst also shows somewhat similar results (entry 2). Next, various Lewis acids catalysts such as Cu(OTf) 2 , Zn(OTf) 2 , Yb(OTf) 3, In(OTf) 3 , Sc(OTf) 3 and Bi(OTf) 3 has been investigated (entries [3][4][5][6][7][8] . The best result was obtained with 5 mol% of Sc(OTf) 3 in MeOH that afforded 2a/3a in 87% yield with good regioselectivity (23:1) (entry 7).…”

Section: Methodsmentioning

confidence: 99%

“…3,4 As a result, the development of reactions involving cleavage of C−C bonds is very difficult to realise and pose serious challenge to synthetic organic chemists. Literature scrutiny revealed that significant progress has been made in the field of this research; however, this chemistry has been mainly limited to ringstrained molecules [5][6][7][8][9][10] and specially designed model compounds. 11,12 Herein, we report Sc(OTf) 3 catalysed C-C bond cleavage in ynones that leads to synthesis of ketones that from ynones would have poor atom economy of ketones.…”

Section: Introductionmentioning

confidence: 99%