A highly enantioselective transformation catalyzed by chiral (acyclic diaminocarbene)gold(I) complexes is reported. The enantioselective synthesis of 2-substituted chromenyl pivalates from racemic phenol-substituted propargyl pivalates was developed. Rearrangement of the substrates in the presence of cationic gold gave allene intermediates, whose cyclization resulted in formation of enantioenri...

The paper describes a convenient and efficient method for regioselective synthesis of phosphorylated α-hydroxyallenes using an atom economical [2,3]-sigmatropic rearrangement of intermediate propargyl phosphites or phosphinites. These can be readily prepared via reaction of protected alkynols with dimethyl chlorophosphite or chlorodiphenyl phosphine respectively in the presence of a base.

A combination of IPrAuNTf(2) as catalyst in the presence of Selectfluor has been successfully used for the high yielding synthesis of α-fluoroenones via 1,3-acyloxy rearrangement of propargyl acetates followed by Csp(2)-F bond formation, likely involving a redox Au(I)/Au(III) catalytic cycle.

The Boyland-Sims Oxidation reaction uses an alkaline solution of peroxydisulfate salt to convert arylamines o-aminophenols. long-standing mechanism involves a nucleophilic attack by the amine leading formation arylhydroxylamine-O-sulfonate intermediate, which then rearranges arylamine o-sulfate. on peroxide oxygen has been questioned Marjanović et al. who have proposed nitrenium ion intermediat...

Catalytic asymmetric [2,3] sigmatropic rearrangement of sulfur ylides generated from aryldiazoacetates and propargyl sulfides with a number of chiral Rh(II) and Cu(I) catalysts have been investigated and moderately high enantioselectivities (up to 81% ee) have been achieved. © 2003 Elsevier Science Ltd. All rights reserved.

A highly stereoselective [2,3]-sigmatropic rearrangement of sulfur ylide generated through Cu(I) carbene and allyl and propargyl sulfides by a double asymmetric induction approach that combines a chiral camphor sultam auxiliary and Cu(I) catalyst with chiral or achiral diimine ligands has been developed.

An efficient synthesis of the 1-hydroxy-2-(prop-2'-enyl)9-anthrone is described. Selective nitration of anthraquinone, reduction to the corresponding amine, diazotization and treatment by sulfuric acid solution afforded the 1-hydroxy-9,10-anthraquinone in good yield as the key intermediate. Reaction with allyl bromide/K2CO3 and subsequent selective reduction accompanie...

Functionalizable monotelechelic polymers are useful materials for chemical biology and materials science. We report here the synthesis of a capping agent that can be used to terminate polymers prepared by ring-opening metathesis polymerization of norbornenes bearing an activated ester. The terminating agent is a cis-butene derivative bearing a Teoc (2-trimethylsilylethyl carbamate) protected pr...

Au-catalyzed rearrangement of alkynes has attracted considerable attention in recent years. In particular, the Au-catalyzed rearrangement of propargyl acetate generates Au–carbene species through 1,2-acetoxy migration. The Au–carbene species thus generated undergoes a variety of transformations. Moreover, Au-catalyzed rearrangement of propargyl acetate to allene through 1,3-shift of the acetoxy...

A series of small molecules containing polar aromatic substituents and alkynes have been synthesized. One–pot preparations an alkynyl imine amide are reported. one-pot preparation a catechol amine was also attempted but in our hands it proved much better to synthesize this target molecule via three step synthesis which we report here.