- Synthesis of β-hydroxyamides through ruthenium-catalyzed hydration/transfer hydrogenation of β-ketonitriles in water: Scope and limitations
-
A cascade process for the straightforward one-pot conversion of β-ketonitriles into β-hydroxyamides is presented. The process, that proceeds in water employing the arene-ruthenium(II) complex [RuCl2(η6-p-cymene){P(4-C6H4F)2Cl}] as catalyst in combination with sodium formate, involves the initial hydration of the β-ketonitrile substrates to generate the corresponding β-ketoamide intermediates, which subsequently undergo the transfer hydrogenation (TH) of the carbonyl group. Employing a family of forty different β-ketonitriles, featuring diverse substitution patterns, the scope and limitations of the process have been established.
- González-Fernández, Rebeca,Crochet, Pascale,Cadierno, Victorio
-
-
- Ruthenium-Catalyzed Synthesis of β-Hydroxyamides from β-Ketonitriles in Water
-
An unprecedented hydration/transfer hydrogenation tandem process for the catalytic conversion of β-ketonitriles into synthetically useful β-hydroxyamides in water has been developed, making use of the ruthenium(II) complex [RuCl2(η6-
- González-Fernández, Rebeca,Crochet, Pascale,Cadierno, Victorio
-
supporting information
p. 6164 - 6167
(2016/12/09)
-
- Highly Stereoselective Reduction of β-Keto Amides: The First General and Efficient Approach to N-mono- and non-Substituted anti-α-Alkyl β-Hydroxy Amides
-
The first general protocol for the anti-selective reduction of α-alkyl-β-keto amides is described. This simple and efficient methodology based on an open-chain Felkin-Anh model pathway, allows the isolation of N-mono- and non-substituted anti-α-substituted β-hydroxy amides in good yields and with high diastereo-selectivity.
- Bartoli, Giuseppe,Bosco, Marcella,Marcantoni, Enrico,Melchiorre, Paolo,Rinaldi, Samuele,Sambri, Letizia
-
-
- The Phenyldimethylsilyl Group as a Masked Hydroxy Group
-
A phenyldimethylsilyl group attached to carbon can be converted into hydroxy group 1->5, with retention of configuration at the migrating carbon, by any of three main methods.The first involves protodesilylation, to remove the phenyl ring from the silicon atom, followed by oxidation of the resulting functionalized silicon atom using peracid or hydrogen peroxide.The second uses mercuric acetate for the same purpose, and can be combined in one pot with the oxidative step using peracetic acid.This method has a variant in which the mercuric ion is combined with palladium(II) acetate, both in less than stoichiometric amounts.The third uses bromine, which can also be used in one pot in conjuction with peracetic acid.In this method, but not in the method based on mercuric acetate, the peracetic acid may be buffered with sodium acetate.The method using bromine as the electrophile for removing the benzene ring has a more agreeable variant in which it is administered in the form of potassium bromide, which is oxidised to bromine by the peracetic acid.The scope and limitations of each of these methods are reported with a range of examples possessing between them many of the common functional groups.Simple benzene rings, alcohols, ethers, esters, amides and nitriles are compatible with all three methods, and ketones do not undergo Baeyer-Villiger reaction under any of the conditions.Amines, however, are oxidised to amine oxides.Ketones may be brominated in the third of the three main species.The absence of acid in the third method makes it especially valuable when the phenyldimethylsilyl group has a neighbouring nucleofugal group such as hydroxy or acetoxy.Carbon-carbon double bonds are incompatible with the methods, except for terminal monosubstituted double bonds, which can survive the conditions used in the first of the three methods.
- Fleming, Ian,Henning, Rolf,Parker, David C.,Plaut, Howard E.,Sanderson, Philip E. J.
-
p. 317 - 338
(2007/10/02)
-