Site-switchable mono-O-allylation of polyols

Palladium-catalyzed mono-N-allylation of unprotected amino acids with 1,1-dimethylallyl alcohol in water.

Palladium-catalyzed N-allylation of unprotected amino acids with 1,1-dimethylallyl alcohol were carried out. The reaction in the presence of Pd(OAc)(2) (5 mol%), sodium diphenylphosphinobenzene-3-sulfonate (TPPMS, 10 mol%), and AcONa (2 equiv) in water at 120 °C for 16 h in a sealed tube gave only mono-N-allylated amino acids in good yield.

Switchable Site-Selective Catalytic Carboxylation of Allylic Alcohols with CO2.

A switchable site-selective catalytic carboxylation of allylic alcohols has been developed in which CO2 is used with dual roles, both facilitating C-OH cleavage and as a C1 source. This protocol is characterized by its mild reaction conditions, absence of stoichiometric amounts of organometallic reagents, broad scope, and exquisite regiodivergency which can be modulated by the type of ligand em...

Sugar reduction with Polyols

Adenosine-5'-O-phosphorylated and adenosine-5'-O-phosphorothioylated polyols as strong inhibitors of (symmetrical) and (asymmetrical) dinucleoside tetraphosphatases.

Dinucleoside 5',5"'- P (1), P ( n )-polyphosphates, and particularly the diadenosine compounds, have been implicated in extracellular purinergic signalling and in various intracellular processes, including DNA metabolism, tumour suppression and stress responses. If permitted to accumulate, they may also be toxic. One approach to understanding their function is through the various specific degra...

Sequential Birch Reduction-Allylation and Cope Rearrangement of O-Anisic Acid Derivatives

A new method for the construction of quaternary centers on cycloalkane rings is reported. The Cope rearrangement of 4methyl-2-allyl-2-(N-pyrrolidinyl)-carboxamide-3-cyclohexenone yields 4-methyl-4allyl-2-(N-pyrrolidinyl)-carboxamide-2-cyclohexenone in high yield. The rearrangement substrates are easily generated from Birch reduction-allylation of o-anisic acid derivatives. © 2012 Elsevier Scien...