Organometallic chemistry and surface science: mechanistic models for the Fischer–Tropsch synthesis

Expansion to seven-membered rings

The reduction of various carbon–nitrogen π-systems to saturated derivatives with metal hydrides, principally aluminum- and boron-based reagents, provides highly useful processes for the preparation of amines and related functionalities.

Reduction of C N to CHNH by Metal Hydrides

Diels−Alder cycloadditions of oximinosulfonate 8 with a variety of 1,3-dienes proceed with regiochemistry opposite to that observed with conventional imino dienophiles, providing expeditious synthetic routes to substituted pyridines, tetrahydropyridines, and pyrrolines. The oximinosulfonate 8 is prepared in one convenient synthetic operation from Meldrum's acid and reacts with conjugated dienes at −78 °C in the presence of 2 equiv of dimethylaluminum chloride to afford [4 + 2] cycloadducts in good to excellent yield. Exposure of these cycloadducts to the action of NaOMe and N-chlorosuccinimide in methanol−THF at room temperature then produces substituted pyridines. The utility of this new two-step annulation protocol is demonstrated in total syntheses of the pyridine alkaloids fusaric acid and (S)-(+)-fusarinolic acid. Heating the [4 + 2] cycloadducts derived from 8 in a mixture of acetonitrile and pH 7 phosphate buffer induces an unusual Stieglitz-type rearrangement leading to the formation of interestin...

Synthesis of Substituted Pyridines via Regiocontrolled [4 + 2] Cycloadditions of Oximinosulfonates

MNDO properties of heteroatom and phenyl substituted nitrenium ions

Solvolyse des derives p-nitrobenzenesulfonyloxy de methyl-2 octyl-2 amine, methyl-1cyclotrexylamine et trimethyl-4,7,7 aza-2 bicyclo [2.2.1] heptane et du derive trifluoromethyl-3 benzenesulfonyloxy de la dibenzylamine. Mise en evidence d'une competition entre 2 types de mecanismes: enlevement d'hydrogene ou transposition

Ionization of N-arylsulfonyloxy amines: the nitrenium ion question

A partir de cyclanylamines (cyclopentyl- et cyclohexylamines), synthese d'imines cycliques a 6 et 7 chainons

Carbon-to-nitrogen rearrangement in N-(arylsulfonoxy)amines as a route to azacyclic compounds

A New Synthesis of Oxime Derivatives from Carbonyl Compounds and N,O-Bis(trimethylsilyl)hydroxylamine

La reaction du titre dans des alcools donne les alcoxy-2 p-nitrobenzenesulfonyloxy-3 perhydro pyrannes La stereochimie du processus d'addition depend de l'encombrement sterique de l'alcool attaquant

Electrophilic addition of p-nitrobenzenesulfonyl peroxide to 3,4-dihydro-2H-pyran

A previously reported laboratory may have reported gas chromatographic separation of the 4-methyl-3-heptanol diastereomiers in error. The side reactions in the Grignard reaction account for the obs...

Gregory A. Buntain

Papers

Ionization of N-arylsulfonyloxy amines: the nitrenium ion question

Carbon-to-nitrogen rearrangement in N-(arylsulfonoxy)amines as a route to azacyclic compounds

A New Synthesis of Oxime Derivatives from Carbonyl Compounds and N,O-Bis(trimethylsilyl)hydroxylamine

Electrophilic addition of p-nitrobenzenesulfonyl peroxide to 3,4-dihydro-2H-pyran

A reinvestigation of the synthesis of 4-methyl-3-heptanol