Amines Isomerism

Remote olefins are maintained in BINAP-Rh(l)-catalyzed allylic amine isomerizations 1. (CH3)2CO, aq. NaOH (aldol condensatlon/dehydratlon) 2. H2, Pt/C... 

Remote hydroxyl groups are compatible with BINAP-Rh(l)-catalyzed allylic amine isomerizations... 

In the Rh-BINAP-catalyzed allyl amine isomerization step used in Takasago s Menthol process, the catalyst is inhibited by water through the formation of a hydroxyl-bridged rhodium trinuclear complex [ Rh(BINAP) i(/<2-0H)2]C104 [61]. 

When the reaction of a triethylsilyl-substituted derivative 42 is examined, an allylic alcohol 43 is isolated albeit in low yield. This result suggests that in the presence of a tertiary amine isomerization of the cyclopropanol to an allylic al-... 

Allylic amide isomerization, 117 Allylic amine isomerization ab initio calculations, 110 catalytic cycle, 104 cobalt-catalyzed, 98 double-bond migration, 104 isotope-labeling experiments, 103 kinetics, 103 mechanism, 103 model system, 110 NMR study, 104 rhodium-catalyzed, 9, 98 Allylnickel halides, 170 Allylpalladium intermediates, 193 Allylsilane protodesilylation, 305 Aluminum, chiral catalysts, 216, 234, 310 Amide dimers, NMR spectra, 282, 284 Amines ... 

Isotope-labeling experiments, amine isomerization, 103 Itatonic acid, 28... 

Organometallic compounds asymmetric catalysis, 11, 255 chiral auxiliaries, 266 enantioselectivity, 255 see also specific compounds Organozinc chemistry, 260 amino alcohols, 261, 355 chirality amplification, 273 efficiency origins, 273 ligand acceleration, 260 molecular structures, 276 reaction mechanism, 269 transition state models, 264 turnover-limiting step, 271 Orthohydroxylation, naphthol, 230 Osmium, olefin dihydroxylation, 150 Oxametallacycle intermediates, 150, 152 Oxazaborolidines, 134 Oxazoline, 356 Oxidation amines, 155 olefins, 137, 150 reduction, 5 sulfides, 155 Oxidative addition, 5 amine isomerization, 111 hydrogen molecule, 16 Oxidative dimerization, chiral phenols, 287 Oximes, borane reduction, 135 Oxindole alkylation, 338 Oxiranes, enantioselective synthesis, 137, 289, 326, 333, 349, 361 Oxonium polymerization, 332 Oxo process, 162 Oxovanadium complexes, 220 Oxygenation, C—H bonds, 149... 

Aliphatic aldehydes and ketones react with aziridines to form relatively stable half aminals, eg, aziridine reacts with formaldehyde to form Ai-hydroxymethylaziridine [20276-43-1]. Half aminals can be converted to full aminals by reaction with a further secondary amine, isomerized to oxazolidines by the action of heat or used in a Mannich reaction for the ring aminomethylation of phenols, although this reaction gives only moderate yields (218-227). 

AUylic alcohols and amines. Isomerization of epoxides to allylic alcohols by Te-NaBH probably involves epitelluride intermediates. Formation of allylic amines from aziridines requires the presence of a sulfonyloxy group at the a-position. 

When a solution of the photostationary mixture of c- and t-24 was treated in the dark by a polar additive such as alcohol or amine, isomerization of t-24 to the starting Z isomer was observed. If the reaction was monitored by circular dichroism in the presence of chiral additives, a dichroic band with a maximum at 335 nm was observed. This ICD band appeared, increased with time, and then disappeared slowly within a few hours, leaving c-24 as the only product (Scheme 9). 

Although no geometries have been indicated in most of these synthetic works, it is known that amines isomerize maleic acid derivatives to the thermodynamically more stable fumaric acid derivatives. Furthermore, cycliz-ation to imides is much more easily obtained with succinic acid and phthalic acid/ It may be concluded, therefore, that low yields of cyclization in maleamic acid is not so much due to lack of reactivity as to the formation of less reactive fumaramic derivative by isomerization. 

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