14366-89-3Relevant academic research and scientific papers
The Chemistry of Enoxysilacyclobutanes: Highly Selective, Uncatalyzed Aldol Additions
Denmark, Scott E.,Griedel, Brian D.,Coe, Diane M.
, p. 988 - 990 (1993)
O-(Silacyclobutyl)ketene acetals derived from esters, thiol esters, and amides reacted with a variety of aldehydes at room temperature without the need for catalysts.The O,O-ketene acetal of E-configuration reacted rapidly to afford the syn aldol products with high diastereoselectivity (93/7 - 99/1).
CHIRAL INDUCTION IN THE CYCLOCONDENSATION OF ALDEHYDES WITH SILOXYDIENES
Bednarski, M.,Maring, C.,Danishefsky, S.
, p. 3451 - 3454 (1983)
Eu(hfc)3 catalyzes the title reaction with substantial asymmetric induction.
Visible-Light-Driven, Metal-Free Divergent Difunctionalization of Alkenes Using Alkyl Formates
Zheng, Ming,Hou, Jing,Zhan, Le-Wu,Huang, Yan,Chen, Ling,Hua, Li-Li,Li, Yan,Tang, Wan-Ying,Li, Bin-Dong
, p. 542 - 553 (2021/01/14)
In recent decades, difunctionalization of alkenes has received considerable attention as an efficient and straightforward way to increase molecular complexity. However, examples of the difunctionalization of alkenes initiated by the intermolecular addition of alkoxycarbonyl radicals providing substituted alkanoates are still rare. Herein, we present the visible light-driven metal-free divergent difunctionalization of alkenes triggered by the intermolecular addition of alkoxycarbonyl radicals under ambient conditions. Employing alkyl formates as precursors of alkoxycarbonyl radicals and 4CzIPN as the photocatalyst, a variety of substituted alkanoates, including β-alkoxy, β-hydroxy, β-dimethoxymethoxy, and β-formyloxy alkanoates, could be facilely accessed with high functional group tolerance and high efficiency. Moreover, the mechanism study revealed that β-hydroxy alkanoates were generated by a selective decomposition of orthoformates promoted by the N-alkoxyazinium salt.
Fe-Catalyzed Anaerobic Mukaiyama-Type Hydration of Alkenes using Nitroarenes
Bhunia, Anup,Bergander, Klaus,Daniliuc, Constantin Gabriel,Studer, Armido
supporting information, p. 8313 - 8320 (2021/03/08)
Hydration of alkenes using first row transition metals (Fe, Co, Mn) under oxygen atmosphere (Mukaiyama-type hydration) is highly practical for alkene functionalization in complex synthesis. Different hydration protocols have been developed, however, control of the stereoselectivity remains a challenge. Herein, highly diastereoselective Fe-catalyzed anaerobic Markovnikov-selective hydration of alkenes using nitroarenes as oxygenation reagents is reported. The nitro moiety is not well explored in radical chemistry and nitroarenes are known to suppress free radical processes. Our findings show the potential of cheap nitroarenes as oxygen donors in radical transformations. Secondary and tertiary alcohols were prepared with excellent Markovnikov-selectivity. The method features large functional group tolerance and is also applicable for late-stage chemical functionalization. The anaerobic protocol outperforms existing hydration methodology in terms of reaction efficiency and selectivity.
Polymer-supported PPh3 as a reusable organocatalyst for the Mukaiyama aldol and Mannich reaction
Matsukawa, Satoru,Fukazawa, Kazuki,Kimura, Junya
, p. 27780 - 27786 (2014/07/21)
An easily accessible and user-friendly polymer-supported phosphine PS-PPh3 catalyzes the aldol reaction of aldehydes and imines. A broad range of aldehydes and imines could be applied under mild conditions using 5-10 mol% PS-PPh3. PS-PPh3 was easily recovered and reused with minimal loss of activity. This journal is the Partner Organisations 2014.
Asymmetric reductive aldol-type reaction with carbonyl compounds using dialkyl tartrate as a chiral ligand
Isoda, Motoyuki,Sato, Kazuyuki,Tokura, Yoriko,Tarui, Atsushi,Omote, Masaaki,Ando, Akira
, p. 956 - 961 (2014/12/11)
An asymmetric reductive aldol-type reaction of α,β-unsaturated esters with carbonyl compounds using Rh catalyst and Et2Zn was investigated. A chiral zinc complex from α,β-unsaturated ester was easily generated as the key intermediate from Et2Zn and Wilkin
Reductive aldol-type reaction of α,β-unsaturated esters with aldehydes or ketones in the presence of Rh catalyst and Et2Zn
Sato, Kazuyuki,Isoda, Motoyuki,Tokura, Yoriko,Omura, Keiko,Tarui, Atsushi,Omote, Masaaki,Kumadaki, Itsumaro,Ando, Akira
, p. 5913 - 5915 (2013/10/21)
The reaction of RhCl(PPh3)3 with Et2Zn easily generated a rhodium-hydride complex (Rh-H) that added to α,β-unsaturated esters to form rhodium enolate complexes by formal 1,4-reduction. These rhodium enolates gave the corre
Regio-and enantioselective bioreduction of methyleneketoesters using both polymeric resin and cellulose matrix
Chaves, Michel R.B.,Moran, Paulo J.S.,Rodrigues, J. Augusto R.
, p. 73 - 77 (2013/11/19)
Methyleneketoesters were prepared in >90% yield by performing an IBX oxidation of Morita-Baylis-Hillman adducts. A methodology was developed to achieve methyl 3-aryl-3-keto-2-methylenepropanoate reduction using a screening of yeast strains in three different reaction procedures to obtain products with both high yield and diastereoselectivity. The reactions conducted in water provided inferior yields (50%) for substrates 2b-c. Employing Amberlite XAD7HP which was a substrate reservoir that also immediately extracted the products from the reaction medium after their formation, syn-4a-c and anti-4a-c were isolated in 60-70% yield, with high stereoselectivity (98-99% ee). The best results were obtained using substrates adsorbed on filter paper which provided products yields above 70%, a 99% ee and a diastereomoeric ratio (syn-4: anti-4) 9:1. Cellulose matrix has excellent potential to be successfully employed in general biocatalytic reactions.
Cyclopropenone catalyzed substitution of alcohols with mesylate ion
Nacsa, Eric D.,Lambert, Tristan H.
supporting information, p. 38 - 41 (2013/03/28)
The cyclopropenone catalyzed nucleophilic substitution of alcohols by methanesulfonate ion with inversion of configuration is described. This work provides an alternative to the Mitsunobu reaction that avoids the use of azodicarboxylates and generation of hydrazine and phosphine oxide byproducts. This transformation is shown to be compatible with a range of functionality. A cyclopropenone scavenge strategy is demonstrated to aid purification.
Solvent- or temperature-controlled diastereoselective aldol reaction of methyl phenylacetate
Ramachandran, P. Veeraraghavan,Chanda, Prem B.
supporting information, p. 4346 - 4349 (2012/10/29)
Unlike the enolboration-aldolization of methyl propanoate, the choice of either the solvent or temperature determines the diastereoselectivity during the enolboration-aldolization of methyl phenylacetate. In CH2Cl 2, the reaction favors the anti-pathway at -78 °C and the syn-pathway at rt. Conversely, the reaction produces the anti-isomer up to rt and the syn-isomer at refluxing temperatures in nonpolar solvents.
