Synthesis of 1,3-Diols by O-Nucleophile Additions to Activated Alkenes

Nucleophile-catalyzed additions to activated triple bonds. Protection of lactams, imides, and nucleosides with MocVinyl and related groups.

Additions of lactams, imides, (S)-4-benzyl-1,3-oxazolidin-2-one, 2-pyridone, pyrimidine-2,4-diones (AZT derivatives), or inosines to the electron-deficient triple bonds of methyl propynoate, tert-butyl propynoate, 3-butyn-2-one, N-propynoylmorpholine, or N-methoxy-N-methylpropynamide in the presence of many potential catalysts were examined. DABCO and, second, DMAP appeared to be the best (high...

Rhenium-catalyzed didehydroxylation of vicinal diols to alkenes using a simple alcohol as a reducing agent.

A new method for the catalytic didehydroxylation of vicinal diols is described. Employing a readily available low-valent rhenium carbonyl complex and a simple alcohol as a reducing agent, both terminal and internal vicinal diols are deoxygenated to olefins in good yield. The optional addition of acid (TsOH, H(2)SO(4)) provides access to lower reaction temperatures. This new system enables the t...

Iridium catalysed synthesis of piperazines from diols.

A green and atom-economical method has been developed for the synthesis of piperazines by cyclocondensation of diols and amines in aqueous media in the presence of a catalytic amount of [Cp*IrCl2]2.

Selective, Radical-Mediated Additions of Thiols to Alkenes in the Presence of Protected Alkynes

Iron-catalyzed radical aryldifluoromethylation of activated alkenes to difluoromethylated oxindoles.

An iron-catalyzed aryldifluoromethylation of activated alkenes under mild reaction conditions has been developed, which is a rare example where a cosolvent is used to improve the reaction yield along with Fenton's reagent and thus provides an economic and green method for the synthesis of a variety of difluoromethylated oxindoles. Preliminary mechanistic investigations indicate a radical additi...