Silver-Mediated Synthesis of Heterocycles

Álvarez-Corral, Míriam; Muñoz‐Dorado, Manuel; Rodrı́guez-Garcı́a, Ignacio

doi:10.1021/cr078361l

Cited by 558 publications

(88 citation statements)

References 226 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A portion of this solution (0.35 ml) was loaded into an amber NMR tube, and 5 equiv. of the corresponding arylboronic acid in CD 3 OD was added to the tube (0.35 ml, 0.12 M). Final concentrations: [1 ClO4 ] ¼ 12 mM and [arylboronic acid] ¼ 60 mM.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

et al. 2014

View full text Add to dashboard Cite

Silver is extensively used in homogeneous catalysis for organic synthesis owing to its Lewis acidity, and as a powerful one-electron oxidant. However, two-electron redox catalytic cycles, which are most common in noble metal organometallic reactivity, have never been considered. Here we show that a Ag(I)/Ag(III) catalytic cycle is operative in model C–O and C–C cross-coupling reactions. An aryl-Ag(III) species is unequivocally identified as an intermediate in the catalytic cycle and we provide direct evidence of aryl halide oxidative addition and C–N, C–O, C–S, C–C and C–halide bond-forming reductive elimination steps at monometallic silver centres. We anticipate our study as the starting point for expanding Ag(I)/ Ag(III) redox chemistry into new methodologies for organic synthesis, resembling well-known copper or palladium cross-coupling catalysis. Furthermore, findings described herein provide unique fundamental mechanistic understanding on Ag-catalysed cross-coupling reactions and dismiss the generally accepted conception that silver redox chemistry can only arise from one-electron processesThis work was supported by grants from the European Research Council (Starting Grant Project ERC-2011-StG-277801), the Spanish MINECO (CTQ2012-37420-C02-01/BQU, CTQ2012-32436, Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT-420000-ACT1) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637

show abstract

Section: Methodsmentioning

confidence: 99%

“…Silver holds the most unexplored chemistry among the coinage metals and its redox chemistry is the least understood [1][2][3][4][5] . Ag(I) salts are commonly employed in organic transformations by exploiting three main properties (Fig.…”

mentioning

confidence: 99%

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

et al. 2014

View full text Add to dashboard Cite

show abstract

“…We have shown that the silver-catalysed [5] cyclisation of allenic hydroxylamines is ap owerful method for the stereocontrolled synthesis of 1,3-aminoalcohols via isoxazolidine intermediates, and this has been demonstratedb yt he synthesis of sedamine, [6] porantheridine, [7] ands edinine. [8,9] We subsequently applied this methodt ot he synthesis of nupharamine 1,a nd the unnamed indolizidine Nuphar alkaloid 3,b oth in racemic form.…”

Section: Resultsmentioning

confidence: 97%

Synthesis of (−)‐Deoxynupharidine by Allenic Hydroxylamine Cyclisation

et al. 2015

View full text Add to dashboard Cite

(À)-Deoxynupharidine has been synthesised via an intermediate that can also be used for other Nuphar alkaloids. Significants teps include the optimisede nzymatic resolution of an allenic alcohol, highly diastereoselective silvercatalysed cyclisation of an allenic hydroxylamine, selective cross-metathesis,d iastereoselectivei ntramolecular reductive amination,a nd stereoelectronically controlled enolate alkylation.

show abstract

“…Good chemoselectivity, good functional group compatibility, stability, are the main features of noble metal complexes which are crucial for application in complex molecular environments. One of the representative examples concerns the synthesis of enantiomerically enriched prolines [4,5,6] through the catalytic enantioselective 1,3-dipolar cycloadditions (1, [7,8,9,10,11,12,13,14]between azomethine ylide and alkenes. In fact, silver and copper catalyzed 1,3-DC are very well known and constitute the most reliable, and direct enantioselective methodology to built up to four stereogenic centers of the resulting proline derivatives [6,15,16,17,18], in only one operation step.…”

Section: Introductionmentioning

confidence: 99%

Coinage metal complexes as chiral catalysts for 1,3-dipolar cycloadditions

Nájera

Sansano

2014

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

In this account, we describe the experience of our research group in the implementation of chiral coinage metal complexes into the efficient enantioselective 1,3-DC of azomethine ylides derived from α-amino acids and azlactones with different dipolarophiles. The corresponding chiral metallodipoles were generated in situ and next focused on the synthesis of highly substituted prolines. For this purpose, privileged ligands such as phosphoramidites and binap with silver(I), gold(I) and copper(II) salts are described. Depending from the ligand and mainly from the metal salt it can be possible to control the facial endo/exo-diasteroselectivity and the enantioselectivity of these types of processes. The synthetic processes are also supported by DFT calculations in order to elucidate the most plausible mechanism and the stereochemical results.

show abstract

Silver-Mediated Synthesis of Heterocycles

Cited by 558 publications

References 226 publications

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

Synthesis of (−)‐Deoxynupharidine by Allenic Hydroxylamine Cyclisation

Coinage metal complexes as chiral catalysts for 1,3-dipolar cycloadditions

Contact Info

Product

Resources

About