Asymmetric cyclopropanation of alkenes and diazocarbonyl insertion into SH bonds catalyzed by a chiral porphyrin Ru(II) complex

Galardon, Erwan; Roué, Séverine; Maux, Paul Le; Simonneaux, Gérard

doi:10.1016/s0040-4039(98)00194-4

Cited by 86 publications

(49 citation statements)

References 13 publications

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“…Better results in terms of enantioselectivity were achieved by using chiral ruthenium, rhodium and cobalt porphyrins 114-117 48,52,53 (Figure 2, type C) reported in Scheme 21 together with the synthesised cyclopropanes 3, 5-8 (Scheme 2) and 44 (Scheme 9). Catalyst 114 was also used to promote the cylopropanation of styrene by DAMP, the desired compound 30 (Scheme 7) was obtained in 92% yield, 97:3 d.r.…”

Section: -Symmetric Catalystsmentioning

confidence: 99%

The ligand influence in stereoselective carbene transfer reactions promoted by chiral metal porphyrin catalysts

2016

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The use of diazo reagents of the general formula NC(R)(R) as carbene sources to create new C-C bonds is of broad scientific interest due to the intrinsic sustainability of this class of reagents. In the presence of a suitable catalyst, diazo reagents react with several organic substrates with excellent stereo-control and form N as the only by-product. In the present report the catalytic efficiency of metal porphyrins in promoting carbene transfer reactions is reviewed with emphasis on the active role of the porphyrin skeleton in stereoselectively driving the carbene moiety to the target substrate. The catalytic performances of different metal porphyrins are discussed and have been related to the structural features of the ligand with the final aim of rationalizing the strict correlation between the three-dimensional structure of the porphyrin ligand and the stereoselectivity of carbene transfer reactions.

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Section: -Symmetric Catalystsmentioning

confidence: 99%

The ligand influence in stereoselective carbene transfer reactions promoted by chiral metal porphyrin catalysts

2016

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“…The results summarized in Table 6 (0.1 mol % catalyst) show that both thiophenols (entries 1-5) and nonaromatic thiols (entries 6 and 7) are converted very quickly and in very high yields into the expected SÀH insertion products, a-thio ethyl ester derivatives (Scheme 12). [8,38] The reactions were very fast (see picture in Scheme 12), and even the less reactive EDP reacted quickly with thiophenol (entries 8 and 9) to provide 20 c.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

Aviv

Gross

2008

Chemistry A European J

130

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A thorough mechanistic investigation has been performed on the reactions of primary and secondary amines with diazoacetates, which proceed uniquely quickly and efficiently when catalyzed by iron(III) corroles and porphyrins. Two major differences in relation to other metal-based catalysts are that the iron complexes are not poisoned by excess amine and that metal-carbene intermediates are apparently not involved in the reaction pathway. The results instead point towards nitrogen ylide intermediates formed by nucleophilic attack of the amines on diazoacetate-coordinated iron complexes. Nitrogen ylides are also formed when allyl- and propargyl-substituted tertiary amines react with diazoacetates, a scenario that smoothly leads to 2,3-rearrangement reaction products with catalytic amounts of the iron(III) complexes. Similar findings regarding the superiority of the iron(III) complexes (in terms of catalyst loading, chemical yields, and reaction conditions) were obtained with thiols (S--H insertion) and sulfides (2,3-rearrangement reactions), which suggest similar mechanisms operate in these cases.

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“…Porphyrins and related species have been used as active and versatile catalysts for various reactions involving oxidations [1,2], hydroxylation [3] and cyclopropanations [4]. Groves et al [5] have first described the iron(III) porphyrin with iodosylbenzene system as a functional model for cytochrome P-450 for hydrocarbon oxidation.…”

Section: Introductionmentioning

confidence: 99%

Epoxidation of Styrene by Fe, Mn, and V Metalloporphyrins Encapsulated Si, Al, Ti And V- Mcm-41

et al. 2008

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Iron(III), Mn(III) and VO(IV) metalloporphyrin complexes have been encapsulated into ordered hexagonal mesoporous molecular sieves. The encapsulation is effective due to the electrostatic attraction of quaternary ammonium sites present in the porphyrin and the Brönsted/ Lewis acid sites present in the mesoporous molecular sieves. These heterogeneous catalysts were catalytically active for the epoxidation of styrene with PhIO exhibiting different selectivity and negligible leaching of active species. The heterogeneous catalysts were reused three times with a slighter decrease in activity but the selectivity patterns were maintained during the recycling experiments.

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Asymmetric cyclopropanation of alkenes and diazocarbonyl insertion into SH bonds catalyzed by a chiral porphyrin Ru(II) complex

Cited by 86 publications

References 13 publications

The ligand influence in stereoselective carbene transfer reactions promoted by chiral metal porphyrin catalysts

The ligand influence in stereoselective carbene transfer reactions promoted by chiral metal porphyrin catalysts

Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

Epoxidation of Styrene by Fe, Mn, and V Metalloporphyrins Encapsulated Si, Al, Ti And V- Mcm-41

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