Stereo- and regioselective palladium-catalyzed 1,4-diacetoxylation of 1,3-dienes

Baeckvall, Jan E.; Bystroem, Styrbjoern E.; Nordberg, Ruth E.

doi:10.1021/jo00198a010

Cited by 303 publications

(114 citation statements)

References 3 publications

Supporting

Mentioning

101

Contrasting

Order By: Relevance

“…The unique ability of BQ to oxidize Pd(0) to Pd(II), compared to other chemical oxidants such as Cu(II) or MnO,, also was observed for the catalyzed acetoxylation of olefins by Backvall et al (14,15). In that work the experimental evidence suggested that BQ was actually coordinated to the Pd(I1).…”

Section: Discussionmentioning

confidence: 75%

Electrode-mediated Wacker oxidation of cyclic and internal olefins

Miller¹,

Wayner²

1992

Can. J. Chem.

View full text Add to dashboard Cite

An improved method for the elcctrode-mcdiated oxidations of olefins by palladium(I1) is dcscribed. Current efficiencies from 80% to 95% werc obtained in oxidations of I-dcccnc, styrene, tt.trtls-2-octcne, and cyclohexene in which pcrchloric acid was added to a chloride-free solution of a palladiun~(I1) acctate catalyst. The palladiunl(0) was reoxidized to palladium(I1) by reaction with catalytic amounts of benzoquinone, which was, in turn, regenerated by anodic oxidation. Addition of varying amounts of pcrchloric acid did not affect the current efficiency but accelerated the oxidation reaction, up to a concentration of approximately 0. I5 M. Thc current efficiency remained high (>80%) over the course of the electrode-mediated oxidations of I-decene, trcltls-2-octcne, and cyclohexenc. At thc end of the reactions. when the substrate was depleted, a drastic dccrease in the current was observed, indicating that the catalytic cycle leading to product was primarily responsible for the electrochemical reaction. It also was shown that the rates of the electrochemical reactions were generally slower than those of homogeneous reactions in which a stoichiometric amount of benzoquinone was used, indicating that the elcctroche~nical regeneration of benzoquinonc was mass transport limited at the highest concentrations of pcrchloric acid. This is in contrast to othcr rcports in the literature that suggested that the homogencous (non-electrochemic:~l) reactions were actually slower. Reasons for the discrepancy betwccn thesc results arc discussed. pour I'ensemble des oxydations assistees par une Clcctrode. A la fin de reactions, lorsqu'il ne reste plus de substrat, on observe une dra~natique diminution du courant qui indique que le cycle catalytique conduisant au produit est le principal responsable de la rtaction Clectrochimique. On a montrC que la vitesse des reactions electrochimiq~~es est g&n&ralement plus lentc que les reactions homogenes dans lesquelles on utilise unc quantitd stocchiornttrique de benzoquinone; ceci i n d i q~~e que, 5 des concentrations ClevCes d'acide perchlorique, la rCgCndration clectrochi~nique de la benzoquinonc est li~nittc par un transport de Iiiasse. Cctte situation est en opposition avcc d'autrcs rapports parus dans la littkrature qui suggeraient que Ics reactions homogiines (non-Clectrocliin~iq~~es) sont clc fait plus Icntcs. On discute des raisons pouvant expliquer ccs diff6rcnces.[Traduit par la redaction]

show abstract

Section: Discussionmentioning

confidence: 75%

Electrode-mediated Wacker oxidation of cyclic and internal olefins

Miller¹,

Wayner²

1992

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…Analogous mechanisms are realized in homogeneous oxidation of various dienes in the presence of Pd complexes and p-benzoquinone oxidizing agent, instead of Te. Oxidation of diene alcohols [56] and substituted conjugated dioleins [57] proceed efectively, but BD reacts with low yield and selectivity.…”

Section: Heterolytic Mechanism Of 14-oxidative Addition To Bdmentioning

confidence: 99%

Reactivity of a Simplest Conjugated Diolefin in Liquid-Phase Oxidation: Mechanisms and Products

Кузнецова¹,

Кузнецова²,

Yakovina³

et al. 2018

Alkenes

View full text Add to dashboard Cite

Ethylene is the simplest member of olein series, but butadiene-1,3 (BD) is the simplest conjugated diolein. In this chapter, we describe liquid-phase oxidations of BD with an emphasis on comparison of the diolein with monooleins. BD interacts with oxygen to form polyperoxide, whose thermal decomposition or hydrogenation leads to the formation of 2-butene-1,4-diol, 3-butene-1,2-diol, or butanediols together with furan and acrolein. BD can be oxidized in polar solvents by radical chain route to form directly the dioxygenates. Metal catalysts are able to control the oxidation by promoting formation of 2-butene-1,4-diol, 4-hydroxybut-2-enal, and furan. PdTe/C catalyst is applied in industry to produce 2-butene-1,4-diol diacetates with selectivity of 98%. The outstanding selectivity of the catalyst is caused by combined action of components in nonradical route and esteriication of inal product in acetic acid. Similar reaction in methyl alcohol yields 1,4-dimethoxy-2-butene, but with lower eiciency. The nonradical mechanism is irmly established for epoxidation of BD with hydrogen peroxide catalyzed by phosphotungstates. The selectivity of BD and hydrogen peroxide conversion to 3,4-epoxy-1-butene around 100% is atained. Analysis of published information and our own studies show many similarities in oxidation of BD and light oleins, which are very useful for understanding the mechanisms.

show abstract

“…The synthesis commenced by converting 1,3-cyclohexadiene (84) into epoxide 86 by using the palladium-catalyzed 1,4-diacetoxylation method developed by Bäckvall et al [51] Thus, oxidation of 84 led to 1,4-diacet- www.chemeurj.org oxycyclohex-2-ene, which was then converted into symmetrical epoxide 86 through acetate removal, olefin epoxidation, and PMB protection. The epoxide moiety in 86 was opened by addition of a cuprate reagent (prepared by treatment of 47 with (2-thienyl)cyanocuprate) at room temperature to afford alcohol 87 in 70 % yield.…”

Section: Chidas Fr65814 and Fumagillol Synthesesmentioning

confidence: 99%

Syntheses of Fumagillin and Ovalicin

Yamaguchi

Hayashi

2010

Chemistry A European J

View full text Add to dashboard Cite

This review focuses on the synthetic strategies used for the construction of fumagillin, ovalicin, and other natural products of this family that are known angiogenesis inhibitors. These compounds are comprised of a cyclohexane framework, two epoxides, and five or six contiguous stereogenic centers. The first total syntheses of fumagillin and ovalicin were reported by Corey in 1972 and 1985, respectively. There were numerous studies directed at these natural products in the decades that followed with many reports appearing in the year 2000 or later. Despite the relatively small size of these molecules, their syntheses highlight the efficient construction of stereogenic centers in organic synthesis.

show abstract

Stereo- and regioselective palladium-catalyzed 1,4-diacetoxylation of 1,3-dienes

Cited by 303 publications

References 3 publications

Electrode-mediated Wacker oxidation of cyclic and internal olefins

Electrode-mediated Wacker oxidation of cyclic and internal olefins

Reactivity of a Simplest Conjugated Diolefin in Liquid-Phase Oxidation: Mechanisms and Products

Syntheses of Fumagillin and Ovalicin

Contact Info

Product

Resources

About