82753-05-7Relevant articles and documents
Synthesis of C11-to-C14 methyl-shifted all-: Trans -retinal analogues and their activities on human aldo-keto reductases
Alvarez, Rosana,Barracco, Vito,De Lera, Angel R.,Domínguez, Marta,Farrés, Jaume,Jiménez, Rafael,López, Susana,Parés, Xavier,Pequerul, Raquel,Rivas, Aurea
supporting information, p. 4788 - 4801 (2020/07/13)
Human aldo-keto reductases (AKRs) are enzymes involved in the reduction, among other substrates, of all-trans-retinal to all-trans-retinol (vitamin A), thus contributing to the control of the levels of retinoids in organisms. Structure-activity relationship studies of a series of C11-to-C14 methyl-shifted (relative to natural C13-methyl) all-trans-retinal analogues as putative substrates of AKRs have been reported. The synthesis of these retinoids was based on the formation of a C10-C11 single bond of the pentaene skeleton starting from a trienyl iodide and the corresponding dienylstannanes and dienylsilanes, using the Stille-Kosugi-Migita and Hiyama-Denmark cross-coupling reactions, respectively. Since these reagents differ by the location and presence of methyl groups at the dienylorganometallic fragment, the study also provided insights into the ability of the different positional isomers to undergo cross-coupling and the sensitivity of these processes to steric hindrance. The resulting C11-to-C14 methyl-shifted all-trans-retinal analogues were found to be active substrates when tested with AKR1B1 and AKR1B10 enzymes, although relevant differences in substrate specificities were noted. For AKR1B1, all analogues exhibited higher catalytic efficiency (kcat/Km) than parent all-trans-retinal. In addition, only all-trans-11-methylretinal, the most hydrophobic derivative, showed a higher value of kcat/Km = 106 000 ± 23 200 mM-1 min-1 for AKR1B10, which is in fact the highest value from all known retinoid substrates of this enzyme. The novel structures, identified as efficient AKR substrates, may serve in the design of selective inhibitors with potential pharmacological interest. This journal is
Rhodium-catalyzed hydroformylation of 1,1-disubstituted allenes employing the self-assembling 6-DPPon system
K?pfer, Alexander,Breit, Bernhard
supporting information, p. 6913 - 6917 (2015/06/08)
Abstract A rhodium-catalyzed hydroformylation of 1,1-disubstituted allenes is reported. Using a RhI/6-DPPon catalyst system, one can obtain β,γ-unsaturated aldehydes in high regio- and chemoselectivity. The Z-configured product is formed with up to >95% selectivity when unsymmetrically 1,1-disubstituted allenes are submitted to the reaction conditions. This is the first time that these interesting building blocks are accessible by hydroformylation of allenes. The utility of this methodology is demonstrated by further transformations of one of the obtained products. β,γ-Unsaturated aldehydes are obtained by a rhodium-catalyzed hydroformylation of 1,1-disubstituted allenes. For unsymmetrically 1,1-disubstituted allenes the Z-configured product is formed in up to about 95% selectivity. This is the first time that these building blocks are accessible by hydroformylation of allenes. The utility of this methodology is demonstrated by further transformations of one of the obtained products.
Improved method for the synthesis of β-carbonyl silyl-1,3-dithianes by the double conjugate addition of 1,3-dithiol to propargylic carbonyl compounds
Mukherjee, Sumit,Kontokosta, Dimitra,Patil, Aditi,Rallapalli, Sivakumar,Lee, Daesung
supporting information; experimental part, p. 9206 - 9209 (2010/03/02)
(Chemical Equation Presented) Base-mediated double conjugate addition of 1,3-propane dithiol to various silylated propargylic aldehydes and ketones allows for an efficient and scalable synthesis of β-carbonyl silyl-1,3-dithianes.
