55089-05-9Relevant articles and documents
Hydroformylation of olefins catalyzed by rhodium complexes with phosphinitecalix[4]arenes
Karakhanov,Kardasheva,Runova,Terenina,Shadrova
, p. 340 - 344 (2007)
Hydroformylation of alkenes with various carbon chain lengths and arylalkenes in the presence of the catalytic system consisting of Rh(acac)(CO)2 and phosphinitecalix[4]arenes was studied. The influence of the P/Rh and substrate/catalyst ratios, temperature, and pressure on the process and the product composition was examined.
Comparison of “on water” and solventless procedures in the rhodium-catalyzed hydroformylation of diolefins, alkynes, and unsaturated alcohols
Alsalahi,Trzeciak
, p. 41 - 48 (2016/07/06)
Catalytic systems containing Rh(acac)(CO)2 or Rh/PAA (PAA?=?polyacrylic acid) and hydrophobic phosphine (PPh3) were used in the hydroformylation of diolefins, alkynes, and unsaturated alcohols under solventless and “on water” conditions. The total yield of dialdehydes obtained from 1,5-hexadiene and 1,7-octadiene reached 99%, and regioselectivity towards linear dialdehydes was higher in the “on water” system. The tandem hydroformylation-hydrogenation of phenylacetylene led to the formation of saturated aldehydes (3-phenylpropanal and 2-phenylpropanal) at 98% conversion with a good regioselectivity towards the linear aldehyde in the “on water” reaction. In contrast, solventless conditions appeared better in the hydroformylation of 1-propen-3-ol. 4-Hydroxybutanal, formed in this reaction with an excellent selectivity, was next transformed to tetrahydrofuran-2-ol via a ring-closure process. Cyclic products were also obtained in hydroformylation of 1-buten-3-ol. In reaction of undec-1-ol and 2-allylphenol linear aldehydes were formed with the yield 69–87%. The hydroformylation of 3-buten-1-ol performed under “on water” conditions showed very good regioselectivity towards a linear aldehyde, 5-hydroxypentanal. Further cyclization of the aldehyde to tetrahydropyran-2-ol was observed.
Terminal olefins to chromans, isochromans, and pyrans via allylic C-H oxidation
Ammann, Stephen E.,Rice, Grant T.,White, M. Christina
supporting information, p. 10834 - 10837 (2014/08/18)
The synthesis of chroman, isochroman, and pyran motifs has been accomplished via a combination of Pd(II)/bis-sulfoxide C-H activation and Lewis acid co-catalysis. A wide range of alcohols are found to be competent nucleophiles for the transformation under uniform conditions (catalyst, solvent, temperature). Mechanistic studies suggest that the reaction proceeds via initial C-H activation followed by a novel inner-sphere functionalization pathway. Consistent with this, the reaction shows reactivity trends orthogonal to those of traditional Pd(0)-catalyzed allylic substitutions.
Ortho-dearomatization of phenols creating all-carbon spiro-bicycles
Zheng, Chao,Wang, Lu,Li, Jingjie,Wang, Leifeng,Wang, David Zhigang
supporting information, p. 4046 - 4049 (2013/09/12)
A range of alkene-linked phenols are generally and reliably dearomatized specifically at their ortho-positions to create all-carbon quaternary stereogenic centers at the corresponding spiro-ring junctions, thus establishing a viable solution to the long-standing synthetic challenge.
Synthesis of aromatic aldehydes by aerobic oxidation of hydroaromatic compounds and diarylalkanes using N-hydroxyphthalimide (NHPI) as a key catalyst
Aoki, Yasuhiro,Sakaguchi, Satoshi,Ishii, Yasutaka
, p. 2497 - 2500 (2007/10/03)
Aerobic oxidation of hydroaromatic compounds and diarylalkanes by N-hydroxyphthalimide (NHPI) under mild conditions afforded the corresponding hydroperoxides in high selectivity. Treatment of the resulting hydroperoxides with sulfuric acid followed by neutralization by a base resulted in phenol and aromatic aldehydes in high selectivity. This method provides a convenient synthetic route to aldehydes involving an aromatic moiety.
Catalytic systems based on sulfocalixarenes in the hydroformylation of alkenes
Karakhanov,Kardasheva,Runova,Terenina
, p. 181 - 183 (2007/10/03)
The hydroformylation of unsaturated compounds was examined in aqueous-organic media using a new catalyst system consisting of acetylacetonatodicarbonylrhodium, triphenylphosphine, and sulfonated calixarenes.
OXYGEN HETEROCYCLES BY SULPHUR YLIDE ANNULATION. X. 3-HYDROXY-3,4,5,6-TETRAHYDRO-2H-1-BENZOXOCINS FROM 2-(4-OXOALKYL)PHENOLS AND DIMETHYLSULPHOXONIUM METHYLIDE
Arnone, Alberto,Bernardi, Rosanna,Bravo, Pierfrancesco,Frigerio, Massimo,Ticozzi, Calimero
, p. 87 - 94 (2007/10/02)
The synthesis of several 3-hydroxy-3,4,5,6-tetrahydro-2H-1-benzoxocins, 7, by dimethylsulphoxonium methylide reaction on 2-(4-oxoalkyl)phenols, 5, obtained in turn from o-benzyloxybenzaldehydes, 1, is reported.The formation of intermediate open-chain oxiranes 6 arising by a transfer of methylene from the ylide to the carbonyl group of the substrate and the highly regiospecific endo intramolecular cyclization to 3-hydroxy-3,4,5,6-tetrahydro-2H-1-benzoxocins, 7, have been followed by 1H NMR spectroscopy.The synthesis of the isomeric 2-hydroxymethyl-2,3,4,5-tetrahydro-1-benzoxepins, 9, from the same 2-(4-oxoalkyl)phenols, through methylenation by triphenylphosphonium methylide and MCPBA oxidation is also reported.Dehydration of the title compounds afforded dihydrobenzoxocins 11 - 13 which, upon catalytic hydrogenation, gave 3,4,5,6-tetrahydro-1-benzoxocins 14.A detailed 1H NMR study allowed assignment of the configurations and the preferred conformations of some tetrahydrobenzoxocins and tetrahydrobenzoxepins trisubstituted on the heterocyclic ring.
