The chemistry of pentavalent organobismuth reagents. Part 8. Phenylation and oxidation of alcohols by tetraphenylbismuth esters

Barton, D. H. R.; Finet, Jean‐Pierre; Motherwell, William B.; Pichon, Clotilde

doi:10.1039/p19870000251

Cited by 28 publications

(13 citation statements)

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“…Bi(V) compounds have been studied extensively as aryl transfer reagents in organic synthesis. [22][23][24][25][26] We have presumed that the reaction proceeds through the intermediacy of Ph 3 BiO, but attempts to isolate that compound or to detect it spectroscopically in solution were not successful. In the absence of the carboxylic acid we observed decomposition and side products rather than the formation of a stable complex.…”

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confidence: 99%

Facile One-Pot Synthesis of Triphenylbismuth(V) Bis(carboxylate) Complexes

2014

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Triphenylbismuth(V) bis(carboxylates), Ph 3 Bi(O 2 CR) 2 (R = 5-Br-2-OH-C 6 H 3-(1), 2-OH-C 6 H 4-(2), 2,6-(OH) 2-C 6 H 3-(3); 3-Me-2-NH 2-C 6 H 3-(4); Ph-(5) and Me-(6)) were obtained from the reaction of triphenylbismuth with hydrogen peroxide and excess carboxylic acid in wet 2-propanol. The synthesis avoids the use of halogens as oxidants and the products crystallize directly from the solution as pure compounds. They crystallize from solution without further need of purification. The structures of 1-5 were confirmed by single crystal X-ray diffraction. Compounds 2 and 5 exhibit a different polymorph than that previously reported in the literature. While all of the Bi(V) compounds adopt a trans-axial trigonal-bipyramidal configuration with the carboxylates in the axial positions, there is considerable variation in the coordination of the carboxylate that ranges from simple monohapto to the mixture of monoand bidentate chelating bonding modes.

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Facile One-Pot Synthesis of Triphenylbismuth(V) Bis(carboxylate) Complexes

2014

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“…Arylation of secondary alcohols on the sugar backbone usually requires leaving‐group preparation, and results in epimerization . A phenyl group was introduced in the O3‐position with an organobismuth(V) reagent in low yield . Transition metal catalyzed alkyl–aryl C−O couplings are usually sensitive to steric hindrance and require high temperatures .…”

Section: Methodsmentioning

confidence: 99%

Efficient O‐Functionalization of Carbohydrates with Electrophilic Reagents

2016

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Novel methodology for O‐functionalization of carbohydrate derivatives has been established using bench‐stable and easily prepared iodonium(III) reagents. Both electron‐withdrawing and electron‐donating aryl groups were introduced under ambient conditions and without precautions to exclude air or moisture. Furthermore, the approach was extended both to full arylation of cyclodextrin, and to trifluoroethylation of carbohydrate derivatives. This is the first general approach to introduce traditionally non‐electrophilic groups into any of the OH groups around the sugar backbone. The methodology will be useful both in synthetic organic chemistry and biochemistry, as important functional groups can be incorporated under simple and robust reaction conditions in a fast and efficient manner.

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“…In contrast, the reaction of bismuth [Bi(V)] reagents with alcohols under basic conditions [BTMG (2) or TMG (1)] gives, exclusively, oxidation [90]. …”

Section: Oxidationmentioning

confidence: 99%

Guanidines in Organic Synthesis

Ishikawa

2009

Superbases for Organic Synthesis

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The chemistry of pentavalent organobismuth reagents. Part 8. Phenylation and oxidation of alcohols by tetraphenylbismuth esters

Cited by 28 publications

References 5 publications

Facile One-Pot Synthesis of Triphenylbismuth(V) Bis(carboxylate) Complexes

Facile One-Pot Synthesis of Triphenylbismuth(V) Bis(carboxylate) Complexes

Efficient O‐Functionalization of Carbohydrates with Electrophilic Reagents

Guanidines in Organic Synthesis

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