Enzyme and Palladium Catalysis as a Powerful Combination in Asymmetric Transformations ofmeso-2-Alkene-1,4-diol Derivatives. Application to Enantiodivergent Synthesis of (R)- and (S)-(2,4-Cycloalkadienyl)acetic Acids

Bäckvall, Jan‐E.; Gatti, R.; Schink, Hans E.

doi:10.1055/s-1993-25862

Cited by 44 publications

(19 citation statements)

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“…11 Although this reaction has been used intramolecularly for the formation of bicycles, only one example of an intramolecular nucleophilic attack of a 34 (3H, s, H-14 carboxylate leading to a monolactone has been described. 12 Therefore, when diacid 6 was treated with Pd(OAc) 2 (10 mol%) in AcOH/acetone and in the presence of benzoquinone, dilactone 7 was obtained in a 70% yield. 8 The last step of the synthetic sequence, the introduction of the Á 9,11 double bond in 7, was achieved by elimination of the 11-phenylselenoxide intermediate 2c (80%).…”

Section: 10mentioning

confidence: 99%

Preparation of bioactive podolactones via a new Pd-catalysed bislactonisation reaction. Synthesis of oidiolactone C

Barrero

Moral

Cuerva

et al. 2000

Tetrahedron Letters

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Section: 10mentioning

confidence: 99%

Preparation of bioactive podolactones via a new Pd-catalysed bislactonisation reaction. Synthesis of oidiolactone C

Barrero

Moral

Cuerva

et al. 2000

Tetrahedron Letters

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“…An asymmetric catalytic 1,4-diacetoxylation was achieved by the use of a chiral BQ as a ligand [74]. (11.37) Meso diacetates obtained from 1,4-diacetoxylation of conjugated dienes have been used for enzyme-catalyzed hydrolysis in enantioselective transformations [79][80][81][82][83][84][85]. Also in this case the stereochemistry of the 1,4-addition can be controlled by variation of the ligand environment.…”

Section: -Diacyloxylationmentioning

confidence: 99%

“…In a similar manner, the diacetates from cyclic dienes were enzymatically hydrolyzed and transformed to the enantiomers of cycloalkadienyl acetic acids (R)-and (S)-58 (Scheme 11.19) [80]. The cycloheptadienylacetic acids from the cyclohexenyl diacetate were subsequently used in intramolecular cis-and trans-1,4-acetoxylactonization (cf.…”

Section: -Diacyloxylationmentioning

confidence: 99%

Palladium‐Catalyzed 1,4‐Additions to Conjugated Dienes

Bäckvall

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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“…An example is the cis-1 ,Cdiacetoxylation of 5carbomethoxycyclohexa-1, 3 In a similar manner, the diacetates from cyclic dienes were enzymatically hydrolyzed and transformed to the enantiomers of diene acids 50 [71]. The diene acids from the sevenmembered ring were subsequently used in intramolecular cis-and trans-1,4acetoxylactonizations (cf.…”

Section: Synthetic Applicationsmentioning

confidence: 99%

“…Diacetates obtained from 1,4-diacetoxylation of conjugated dienes have been used for enzymatic hydrolysis in enantioselective transformations[70][71][72][73][74][75]. In an application toward the carpenter bee pheromone (Scheme 8-16), [70] the meso-diacetate 46, obtained from stereoselective 1,4-diacetoxylation of (E,Z)-hexa-2,4-diene, hydroxyacetate 47 in 92% ee.…”

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confidence: 99%

Palladium‐Catalyzed 1,4‐Additions to Conjugated Dienes

Bäckvall¹

1998

Metal‐Catalyzed Cross‐Coupling Reactions

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Additions to nonactivated olefins and dienes are important reactions in organic synthesis [ 11. Although cycloadditions may be used for additions to double bonds, the most common way to achieve such reactions is to activate the olefins with an electrophilic reagent. Electrophilic activation of the olefin or diene followed by a nucleophilic attack at one of the sp2 carbon atoms leads to a 1,2-or lA-addition. More recently, transition metals have been employed for the electrophilic activation of the double bond [2]. In particular, palladium(I1) salts are known to activate carbon-carbon double bonds toward nucleophilic attack [3] and this is the basis for the Wacker process for industrial oxidation of ethylene to acetaldehyde [4]. In this process, the key step is the nucleophilic attack by water on a (n-ethy1ene)palladium complex.Additions to conjugated dienes constitute a special class of reactions, in which it is of great importance to control the regioselectivity toward 1,2-or 1,4-addition. With classical electrophilic reagents, it is difficult to control the regioselectivity: often, mixtures of 1,2and 1,4-regioisomers are formed. With the use of transition metals, highly regioselective additions to conjugated dienes can sometimes be obtained [5]. From a synthetic point of view, this regioselectivity is of great importance if these additions are catalyzed by the metal. One metal that has been successfully used in this respect is palladium. Several reviews have included palladium-catalyzed additions to conjugated dienes [5-101. The present review deals with palladium-catalyzed reactions leading to selective bis-couplings in the 1and 4-positions of 1,3-dienes.Palladium-catalyzed 1,4-additions to conjugated dienes can be divided into two classes: (1) non-oxidation reactions that (2) oxidation reactions. In the former class, a palladium(0) catalyst is employed and the first step in the catalytic cycle is often an activation of one of the reactants by its oxidative addition to Pd(0). In the second class, a palladium(I1) complex is the active catalyst which oxidizes the substrate diene with formation of Pd(0). Reoxidation of Pd(0) to Pd(II) by an oxidant regenerates the active catalyst. Palladium(0)-catalyzed ReactionsThese are non-oxidation reactions that can be divided into several subclasses. The active catalyst is a palladium(0) complex, such as Pd(PPh,), or some analogous phosphine complex. Such palladium(0)-phosphine complexes may also be generated in situ fromMetal-catalyzed Cross-coupling Reactions Edited by François Diederich, Peter J. Stang 340 8 Palladium-catulyzed 1,4-Additions the latter case Pd(I1) is reduced to Pd(0) by the phosphine [ 111. A common feature of the palladium(0)-catalyzed additions to conjugated dienes is that they begin with an oxidative addition of a species such as H-Nu or RX to palladium(0) to give a pdlladium(l1)-hydride complex or an organometallic R-Pd(I1) complex, respectively. These complexes subsequently react with the conjugated diene in a migratory insertion reaction to give...

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Enzyme and Palladium Catalysis as a Powerful Combination in Asymmetric Transformations ofmeso-2-Alkene-1,4-diol Derivatives. Application to Enantiodivergent Synthesis of (R)- and (S)-(2,4-Cycloalkadienyl)acetic Acids

Cited by 44 publications

References 0 publications

Preparation of bioactive podolactones via a new Pd-catalysed bislactonisation reaction. Synthesis of oidiolactone C

Preparation of bioactive podolactones via a new Pd-catalysed bislactonisation reaction. Synthesis of oidiolactone C

Palladium‐Catalyzed 1,4‐Additions to Conjugated Dienes

Palladium‐Catalyzed 1,4‐Additions to Conjugated Dienes

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