Stereochemistry of the solvolysis of menthyl tosylate. Example of retained chair conformation in the transition state

HIRSL-STARCEVIC, S.; Majerski, Zdenko; Sunko, Dionis E.

doi:10.1021/ja00818a056

Cited by 14 publications

(8 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Noteworthy, all these reactions proceed with retention of configuration. The stereochemical outcome observed in this substrate has been previously described 13,14. It is attributed to the formation of a carbocation or ion pair and is the conformation of the menthyl framework and not the leaving group that determines the resultant stereochemistry of the product 15…”

Section: Resultssupporting

confidence: 53%

Iron(III)‐Catalyzed Halogenations by Substitution of Sulfonate Esters

et al. 2011

View full text Add to dashboard Cite

A novel halogenation reaction from sulfonates catalyzed by ironA C H T U N G T R E N N U N G (III) is described. The reaction can be performed as a stoichiometric or a catalytic version. This reaction provides a convenient strategy for the efficient access to structurally diverse secondary chlorides, bromides and iodides. The stereochemical course of the reaction is governed by the substrate and the experimental conditions. Secondary alcohols modified as quisylates or pysylates are substantially more reactive. Aliphatic quisylates proceed with overall inversion of configuration under catalytic conditions. Chemoselectivity in bismesylates was observed in favour of the secondary mesylate. Additionally, based on the experimental results, a possible catalytic cycle for the halogenation has been proposed.

show abstract

Section: Resultssupporting

confidence: 53%

Iron(III)‐Catalyzed Halogenations by Substitution of Sulfonate Esters

et al. 2011

View full text Add to dashboard Cite

show abstract

“…For example, Sunko and his co-workers studied the solvolysis of menthyl tosylate in 70% aqueous ethanol and 70% TFE and found that the products which would be expected for a solvent-assisted reaction (whether direct displacement or elimination) constitute only a small proportion of the total products. 23 Whether or not this ionization may be assisted by neighboring participation is not known.…”

Section: Resultsmentioning

confidence: 99%

Contrasting responses in aqueous trifluoroethanol and aqueous ethanol as a probe for nucleophilic solvent assistance in solvolysis

Raber¹,

Neal²,

Dukes³

et al. 1978

J. Am. Chem. Soc.

View full text Add to dashboard Cite

“…All emission and excitation spectra are corrected; bandpass of both monochromators is 8.5 nm. (11) Typically, absorption of monolayers of I on either hydrophilic glass or cadmium arachidate layers have the same maxima (±5 nm) and extinction (±2.0 X 10-4 OD/layer). By rinsing such slides with THF/CHCI3 and subsequent LC analysis, we have demonstrated recovery of unchanged I; since Journal of the American Chemical Society / 99:4 j February recovery is not yet quantitative, this observation is of uncertain significance.…”

Section: Tris(22'-bipyridine)ruthenium(ii)2+mentioning

confidence: 99%