Marcus A. Tius

Traceless Chiral Auxiliaries for the Allene Ether Nazarov Cyclization

The key stereochemical factors that determine transfer of asymmetry from the chiral auxiliary to the cyclopentenone in the allene ether version of the Nazarov reaction have been elucidated. On the basis of the new insights into the mechanism, two highly effective chiral auxiliaries were designed and prepared.

1-diphenylphosphonio-1-methoxymethyllithium, a useful reagent for the synthesis of aldehydes from hindered ketones

Abstract A new reagent, 1-diphenylphosphonio-1-methoxymethyllithium, has been found to be highly effective for the transformation R2CO → R2CHCHO with sterically hindered, enolizable ketones.

Cinnamyl as a protecting group. A mild method for the cleavage of cinnamyl esters.

Ester des Zimtalkohols (I) reagieren unter schonenden Bedingungen mit Hg-acetat und Methanol zu den Mercuri-Verbindungen (II), die mit Kaliumrhodanid glatt in die entsprechenden Carbonsauren (III) und den Allylather (IV) zerlegt werden.

Gas phase and solution structures of 1-methoxyallenyllithium.

A combined computational and (13)C NMR study was used to determine the solution structures of 1-methoxyallenyllithium. The gas phase calculations indicated that this species is aggregated as a hexamer. The NMR spectra in THF solution, together with the calculated aggregation energies and chemical shifts, are consistent with a dimer-tetramer equilibrium.

A convenient synthesis of (–)-11-nor-Δ9-tetrahydrocannabinol-9-methanol

A convenient enantiospecific total synthesis of (–)-11-nor-Δ9-tetrahydrocannabinol-9-methanol, a human urinary metabolite of Δ9-tetrahydrocannabinol, has been accomplished in six steps from (R)-(+)-perillaldehyde.

Synthetic confirmation of the absolute stereochemistry at C(10), C(11), and C(13) of palytoxin

The absolute stereochemistry at C(10), C(11), and C(13) of palytoxin has been determined by NMR spectroscopy and circular dichroism.