Fast Aldol-Tishchenko Reaction Utilizing 1,3-Diol Monoalcoholates as the Catalysts

Törmäkangas, Olli P.; Koskinen, Ari M. P.

doi:10.1021/op0001335

Cited by 22 publications

(18 citation statements)

References 12 publications

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“…Using a molar ratio [2] : [3] : [4] = 1 : 100 : 100, the product ratio [5] : [6 ] proved to be strongly temperature dependent (Table 1). For the interpretation we have to take into consideration the fact that the trioxane formation is known to be reversible and distinctively dependent on the solvent [6,9,10] as well as the fact that the equilibrium 3 RCHO Ð (RCHO) 3 is shifted to the left with higher temperatures (for R=H, Et see ref.…”

Section: Resultsmentioning

confidence: 99%

“…These reactions can be catalyzed by acids, bases and main group metal alkoxides, respectively [1]. Later on, the catalytic activity of transition metal complexes was recognized and, nowadays, both such homogeneous and heterogeneous catalytic systems for these reactions are established [2][3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

“…Crystal data and structure refinement for (7) and (8) (2) 70.47(2) b,°94.18 (2) 88.11(2) c,°102.02 (2) 76.29(2) V, Å 3 1918.0(6) 1857.7(6) Z 2 2 q cal , g/cm 3 1 …”

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confidence: 99%

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Ruthenium Catalyzed Reactions of Aldehydes: Molecular Structures of Ruthenium Complexes with Aldehyde Ligands

Sorkau

Wagner

Steinborn

et al. 2005

Transition Met Chem

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RuCl(H)(CO)(PPh 3 ) 3 ](2) was found to catalyze, in the presence of H 2 C=CHSiMe 3 (3), the trimerisation of aldehydes RCHO [R=Et (4a), i-Bu (4b)] yielding 1,3,5-trioxanes (5) and the aldol condensation yielding a,b-unsaturated aldehydes (6). When (4a) was used as a reactant, from these reaction mixtures, the ruthenium complex [RuCl 2 (CO)(PPh 3 ) 2 (EtCH@CMeACHO-jO)] (7) having the aldol condensation product as the ligand crystallized. In the analogous reaction with (4b), the complex [RuCl 2 (CO)(PPh 3 ) 2 (i-BuCHO-jO)] (8) with the aldehyde as ligand was obtained. The constitution of these complexes was established by single-crystal X-ray diffraction measurements. The ruthenium centers are octahedrally coordinated having the aldehyde and the carbonyl ligand in mutually trans positions (coordination index: OC-6-12). The aldehydes are monodentately coordinated via the carbonyl oxygen atom (jO). The coordination induced elongations of the C@O double bonds [1.242(4) Å (7), 1.234(4) Å (8)] indicate an activation of the aldehydes. Furthermore, the RuACO bond lengths [1.842(4) Å (7), 1.823(4) Å (8)] exhibit a relatively low trans influence of the aldehyde ligands. The formation of the complexes (7) and (8) give an indication that the Lewis acidity of the ruthenium center is of importance for aldehyde activation in the catalytic process.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ruthenium Catalyzed Reactions of Aldehydes: Molecular Structures of Ruthenium Complexes with Aldehyde Ligands

Sorkau

Wagner

Steinborn

et al. 2005

Transition Met Chem

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“…The reactor consists of two twisted tubes in a helix format to create strong internal circulation (radial mixing) to enhance heat transfer at low Reynolds numbers. The fast preparation 1,3-diol monoesters has been carried out in microreactors with the rapid water-free method in the presence of monoalcoholates of 1,3-diols as catalysts [91] . The new process with the microstructured reactor resulted in fast and clean reactions as compared to the old process which uses several inorganic catalysts.…”

Section: Motionless Mixer Technologymentioning

confidence: 99%

Process intensification in green synthesis

Kumar

Nigam

2012

Green Processing and Synthesis

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In the past few decades there has been an extensive increase in the research for green synthesis processes due to environmental concerns, industrial safety and sustainable development, which makes it an attractive alternative to the conventional synthesis processes. The interest of researchers in the green synthesis processes highlights the importance of understanding the mechanism and the fundamental differences between the different processes. The number of publications in the fi eld of " Green Synthesis " in journals, proceedings, patents, etc. has increased by almost 20 times from 2001 to 2010. The published reports are mainly concerned with green synthesis with catalytic processes, less harmful solvents and process intensifi ed techniques. In the present article, the technological development efforts in the area of green synthesis are summarized. Various techniques for green synthesis process intensifi cation are discussed, e.g., mixers, microreactors, spin disc reactor, oscillated fl ow reactors, microwave irradiation, ultrasonication, multifunctional membranes and coiled fl ow inverter. The applications of green synthesis processes for biofuel, nanoparticle, ionic liquids and pharmaceutical production are also discussed.

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“…Having exhausted the standard arsenal of oxidants (53) by using model system (ϩ)-33 (Scheme 8), we turned to an unorthodox implementation of the Evans-Tishchenko reaction (54,55). This transformation, most often viewed as the reduction of a ␤-hydroxy ketone to the corresponding trans-1,3-diol system, involves intramolecular hydride transfer to generate the ␤-hydroxyl carrying a sacrificial acyl group.…”

Section: Union Of the Northern And Southern Hemispheres Of (؉)-13-deomentioning

confidence: 99%

A unified approach to the tedanolides: Total synthesis of (+)-13-deoxytedanolide

Smith

Adams

Barbosa

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

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A unified approach for the construction of the potent marine antitumor agents (؉)-tedanolide (1) and (؉)-13-deoxytedanolide (2) is described. Highlights of the synthetic strategy include the development of a versatile bifunctional dithiane-vinyl iodide linchpin, the unorthodox use of the Evans-Tishchenko reaction, and a late-stage high-risk stereocontrolled introduction of the C(18,19) epoxide to achieve a total synthesis of (؉)-13-deoxytedanolide (2).

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Fast Aldol-Tishchenko Reaction Utilizing 1,3-Diol Monoalcoholates as the Catalysts

Cited by 22 publications

References 12 publications

Ruthenium Catalyzed Reactions of Aldehydes: Molecular Structures of Ruthenium Complexes with Aldehyde Ligands

Ruthenium Catalyzed Reactions of Aldehydes: Molecular Structures of Ruthenium Complexes with Aldehyde Ligands

Process intensification in green synthesis

A unified approach to the tedanolides: Total synthesis of (+)-13-deoxytedanolide

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