Bismuth(III) acetate: a cheap, efficient, and environmentally acceptable reagent for ‘wet’ and ‘dry’ prevost reactions

Abstract

cis-and trans-Diol derivatives can be prepared from alkenes by reaction with bismuth(iii) acetate in 'wet' and 'dry' acetic acid respectively.Bismuth(rr1) acetate can be used in both the 'wet' and 'dry' Prevost1.2 reactions as shown in Scheme 1.Bismuth( HI) acetate was prepared either by literature methods from bismuth(rI1) nitrate3 or in situ from cheap and readily available bismuth(I1r) oxycarbonate, (Bi0)2C03. It is also commercially available. In a typical 'dry' reaction, bismuth oxycarbonate (12.3 mmol) was heated under reflux for 1 h with freshly dried acetic acid (40 cm3) containing acetic anhydride (ca. 17%). Cyclohexene (36.6 mmol) and iodine (37.0 mmol) were added to the cooled solution and the mixture was refluxed for 17.5 h. trans-l,2-Diacetoxycyclohexane was obtained in good yield (8O%, after distillation) and no trace of the cis-diacetate could be detected by .A typical 'wet' reaction used similar quantities of reagents except that Laboratory Reagent grade acetic acid (containing ca. 0.6% w/w water) was used and sufficient water (2.5 cm3) was added to the freshly prepared solution of bismuth(Ir1)

Cohalogenation of alkenes with DMF: an easy vicinal haloformyloxylation reaction

“…The formation of the halohydrins could be rationalized by hydrolysis of the haloformate or its precursors during the work up. 6 Alternatively, its formation by addition of water to the halonium ion seems to be improbable because, although we have used DMF without further purification and in an open flask, no loss of stereoselectivity in the reactions of cyclohexene (arising from small amounts of water 22 ) was detected either.…”

Utilisations récentes de dérivés du bismuth en synthèse organique

“…L'acétate de bismuth (III) peut, en présence d'iode moléculaire, conduire à la diacétylation stéréosélective des oléfines [61]. Lorsque la réaction est réalisée dans l'acide acétique glacial, la formation du transdiacétate est effectivement observée de façon sélective.…”

Fe2(SO4)3-mediated Coiodination of Alkenes with Acetic Acid: A Convenient and Regioselective Eco-friendly Preparation of β-iodoacetates

“…2,8 No significant amounts of vicinal diiodoalkanes, diols, iodohydrins or diacetates were detected in the crude products and although we have used acetic acid without further purification in an open flask, no loss of stereoselectivity in the reaction of cyclohexene arising from small amounts of water was detected either. 20 On the other hand, coiodination of styrene with acetic acid in the absence of the Fe(III) salt was disappointing, as several products were obtained along with unreacted substrate. However, the reaction in the absence of any metal salt was successfully achieved with 2 mol equiv.…”