Organomercurials in organic synthesis

Cited by 123 publications

(16 citation statements)

References 291 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The Grignard reaction is a fundamental transformation in chemical synthesis and has been continuously developed over the past century. Its importance is attributed to the reaction's versatility and capacity to form C-C bonds, leading to the formation of secondary and tertiary alcohols [2][3][4][5][6][7] . A key limitation of this reaction, however, is its instability and broad reactivity.…”

mentioning

confidence: 99%

Empowering alcohols as carbonyl surrogates for Grignard-type reactions

Wang

Sim

et al. 2020

Nat Commun

View full text Add to dashboard Cite

The Grignard reaction is a fundamental tool for constructing C-C bonds. Although it is widely used in synthetic chemistry, it is normally applied in early stage functionalizations owing to poor functional group tolerance and less availability of carbonyls at late stages of molecular modifications. Herein, we report a Grignard-type reaction with alcohols as carbonyl surrogates by using a ruthenium(II) PNP-pincer complex as catalyst. This transformation proceeds via a carbonyl intermediate generated in situ from the dehydrogenation of alcohols, which is followed by a Grignard-type reaction with a hydrazone carbanion to form a C-C bond. The reaction conditions are mild and can tolerate a broad range of substrates. Moreover, no oxidant is involved during the entire transformation, with only H2 and N2 being generated as byproducts. This reaction opens up a new avenue for Grignard-type reactions by enabling the use of naturally abundant alcohols as starting materials without the need for pre-synthesizing carbonyls.

show abstract

mentioning

confidence: 99%

Empowering alcohols as carbonyl surrogates for Grignard-type reactions

Wang

Sim

et al. 2020

Nat Commun

View full text Add to dashboard Cite

show abstract

“…Ge, Sn, Pb) and also mercury and thallium have all been employed successfully in halogenating aromatic compounds (2) with chlorine, bromine, and iodine. There is, however, a paucity of information in the literature on the fluorination of organometallic conipounds (3,4) and also on the use of organometallic compounds, containing the metals listed above, in radiohalogen labelling (5)(6)(7). This has prompted us to investigate the utility of these metals in developing a general method for activating aromatic rings toward fluorination for the purpose of labelling with I8F.…”

Section: Introductionmentioning

confidence: 99%

The cleavage of aryl-metal bonds by elemental fluorine: synthesis of aryl-fluorides

Adam¹,

Berry²,

Hall³

et al. 1983

Can. J. Chem.

View full text Add to dashboard Cite

The reaction of elemental fluorine with phenyl derivatives of tin, lead, germanium, silicon, mercury, and thallium has been studied with the aim of developing a general method for labelling aromatic compounds with radioactive 18F. Rapid synthesis of fluorobenzene was achieved in varying chemical yields up to 70%, depending largely upon the metal substrate used, with aryl–tin compounds giving the highest yields. Radiochemical yields are also given for the synthesis of 18F-fluorobenzene from the cleavage of aryl–tin bonds with 18F-F2.

show abstract

“…The ability of these compounds to accommodate a wide variety of functional groups and to tolerate quite diverse reaction conditions is well documented (3). Of the various processes involving organomercurials, solvomercuration-demercuration is the most widely used in organic synthesis (4).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 1-alkoxy-1,2,3,4-tetra-hydrocarbazoles by mercury(II) mediated heterocyclization of 2-cyclohex-2′-enyl-N-alkylanilines

Majumdar¹,

Das²

1996

Can. J. Chem.

View full text Add to dashboard Cite

Abstract:The title compounds 3(a-i) were synthesized in high yields by the mercury(I1) mediated heterocyclization of 2-cyclohex-2'-enyl-N-alkylanilines 2(a-g), which in turn were obtained by the acid-catalyzed amino Claisen rearrangement of 3-N-alkylanilinocyclohexenes l(a-g). Additional supporting evidence for the structure of product 3 was obtained from chemical transformations.Key words: 1-alkoxy tetrahydrocarbazole, mercury(I1) mediated heterocyclization, amino Claisen rearrangement, 3-Nmethylanilinocyclohexene.RCsumC : On a synthttisC les composCs mentionnCs dans le titre, 3a-i, avec des rendements Clevis par le biais de I'httCrocyclisation catalysCe par le mercure(I1) de (2-cyclohex-2'-Cnyl)(N-alkyl)anilines, 2a-g, qui ont CtC par ailleurs obtenues par un riarrangement amino de Claisen, catalysC par les acides, des 3-N-alkylanilinocyclohexknes, la-g. Des transformations chimiques ont permis d'obtenir des donnees additionnelles relatives B la structure du produit 3.

show abstract

Organomercurials in organic synthesis

Cited by 123 publications

References 291 publications

Empowering alcohols as carbonyl surrogates for Grignard-type reactions

Empowering alcohols as carbonyl surrogates for Grignard-type reactions

The cleavage of aryl-metal bonds by elemental fluorine: synthesis of aryl-fluorides

Synthesis of 1-alkoxy-1,2,3,4-tetra-hydrocarbazoles by mercury(II) mediated heterocyclization of 2-cyclohex-2′-enyl-N-alkylanilines

Contact Info

Product

Resources

About