85736-11-4Relevant academic research and scientific papers
Enantioselective construction of tetrasubstituted stereogenic carbons through bronsted base catalyzed michael reactions: α′-hydroxy enones as key enoate equivalent
Badiola, Eider,Fiser, Bla,Gmez-Bengoa, Enrique,Mielgo, Antonia,Olaizola, Iurre,Urruzuno, Iaki,Garca, Jess M.,Odriozola, Jos M.,Razkin, Jess,Oiarbide, Mikel,Palomo, Claudio
, p. 17869 - 17881 (2014)
Catalytic and asymmetric Michael reactions constitute very powerful tools for the construction of new C-C bonds in synthesis, but most of the reports claiming high selectivity are limited to some specific combinations of nucleophile/electrophile compound types, and only few successful methods deal with the generation of all-carbon quaternary stereocenters. A contribution to solve this gap is presented here based on chiral bifunctional Bronsted base (BB) catalysis and the use of α′-oxy enones as enabling Michael acceptors with ambivalent H-bond acceptor/donor character, a yet unreported design element for bidentate enoate equivalents. It is found that the Michael addition of a range of enolizable carbonyl compounds that have previously demonstrated challenging (i.e., α-substituted 2-oxindoles, cyanoesters, oxazolones, thiazolones, and azlactones) to α′-oxy enones can afford the corresponding tetrasubstituted carbon stereocenters in high diastereo- and enantioselectivity in the presence of standard BB catalysts. Experiments show that the α′-oxy ketone moiety plays a key role in the above realizations, as parallel reactions under identical conditions but using the parent α,β-unsaturated ketones or esters instead proceed sluggish and/or with poor stereoselectivity. A series of trivial chemical manipulations of the ketol moiety in adducts can produce the corresponding carboxy, aldehyde, and ketone compounds under very mild conditions, giving access to a variety of enantioenriched densely functionalized building blocks containing a fully substituted carbon stereocenter. A computational investigation to rationalize the mode of substrate activation and the reaction stereochemistry is also provided, and the proposed models are compared with related systems in the literature.
Copper-catalyzed enantioselective conjugate addition of dialkylzinc reagents to α′-oxy enones
Garcia, Jesus M.,Gonzalez, Alberto,Kardak, Bharat G.,Odriozola, Jose M.,Oiarbide, Mikel,Razkin, Jesus,Palomo, Claudio
supporting information; experimental part, p. 8768 - 8771 (2009/10/01)
The copper-catalyzed enantioselective conjugate addition of dialkylzinc reagents to α'-oxy enones was investigated. Cu(OTf)2, ligand, and toluene were placed in a flame-dried Schlenk tube. the resulting mixture was stirred at room temperature f
A Novel and Practical Synthetic Method of 3(2H)-Furanone Derivatives
Sakai, Takashi,Yamawaki, Akitoshi,Ito, Hiroshi,Utaka, Masanori,Takeda, Akira
, p. 1199 - 1201 (2007/10/02)
A novel convenient synthetic method of 5-aryl-2,2-dimethyl-3(2H)-furanones (aryl = C6H5, 2-CH3C6H4, 3-CH3C6H4, 4-CH3C6H4, 2-ClC6H4, 4-ClC6H4, 2,4-Cl2C6H3) is described.It involves the Claisen-Schmidt condensation (potassium hydroxide/ethanol) of aromatic
Stereoelectronic Control of Intramolecular Michael Addition Reactions
Ellis, Graham W. L.,Johnson, C. David,Rogers, David N.
, p. 5090 - 5095 (2007/10/02)
Concepts of stereoelectronic control lead to the conclusion that the 5-endo-trig ring closure of (E)-2-methyl-3-oxo-5-phenylpent-4-en-2-ol should be disfavored.However, the acid-catalyzed ring closure in trifluoroacetic acid occurs readily, suggesting an
