The alkylation process is an important reaction used in refineries to upgrade light olefins and isobutene into a much more highly valued gasoline component. The primary alkylation reaction involves the reaction of isobutene with a light olefin such as butylenes, in the presence of strong acid catalyst to form the high octane. A problem of long standing is to determine the optimal operating cond...

The enantioselective α-vinylation of aldehydes using vinyl iodonium triflate salts has been accomplished via the synergistic combination of copper and chiral amine catalysis. These mild catalytic conditions provide a direct route for the enantioselective construction of enolizable α-formyl vinylic stereocenters without racemization or olefin transposition. These high-value coupling adducts are ...

An iron-catalyzed enantioselective and diastereoselective intramolecular olefin aminochlorination reaction is reported (ee up to 92%, dr up to 15 : 1). In this reaction, a functionalized hydroxylamine and chloride ion are utilized as nitrogen and chlorine sources, respectively. This new method tolerates a range of synthetically valuable internal olefins that are all incompatible with existing a...

We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands that catalyze highly Z-selective olefin metathesis. A very simple and convenient procedure for the synthesis of such catalysts has been developed. Intramolecular C-H bond activation of the NHC ligand, promoted by anion ligand substitution, forms the appropriate chelate for stere...

An efficient rhodium/olefin-sulfoxide catalyzed asymmetric conjugate addition of organoboronic acids to a variety of nitroalkenes has been developed, where 2-methoxy-1-naphthyl sulfinyl functionalized olefin ligands have shown to be highly effective and are applicable to a broad scope of aryl, alkyl, and heteroaryl nitroalkenes.

A highly diastereoselective, visible-light-induced [3 + 2] cycloaddition between N-sulfonyl cyclopropylamines and electron-deficient olefins is reported. The reactions proceed via the oxidation of a sulfonamide aza-anion by an organic photocatalyst to generate nitrogen-centered radical. Strain-induced ring opening intermolecular addition olefin intermediate carbon-centered radical that reduced ...

The ground-breaking advances in catalytic olefin metathesis by Grubbs and others have revolutionized many aspects of organic synthesis, ensuring a high general level of interest in the key metal alkylidene catalysts. The mechanism of ruthenium-mediated olefin metathesis catalysed by first (1a) and second generation (1b) Grubbs complexes has been extensively studied both by experiment and by com...

A highly selective method for the synthesis of asymmetrically substituted carbocycles and heterocycles from unactivated aldehyde-olefin precursors has been achieved via enantioselective SOMO-catalysis. Addition of a catalytically generated enamine radical cation across a pendent olefin serves to establish a general asymmetric strategy toward the production of a wide range of formyl-substituted ...

Oxidative annulations for the synthesis of carbocycles were developed using a catalytic palladium(II) system. Indoles with pendant olefin tethers were oxidatively cyclized to form annulated products. Electron-rich aromatic systems were also investigated, culminating in the synthesis of benzofurans and dihydrobenzofurans by a similar protocol. These reactions were demonstrated to proceed by an i...