Search results for "selective synthesis"
showing 10 items of 430 documents
Mandelamide-zinc-catalyzed enantioselective alkyne addition to heteroaromatic aldehydes.
2006
The (S,S)-mandelamide III catalyzes the additions of both aryl- and alkylalkynylzinc reagents to heteroaromatic aldehydes with good yields and enantioselectivities up to 92%. This catalyst is easily prepared in a one-step procedure, and both enantiomers are available. Unlike most other described methods, using this catalyst does not require the addition of Ti(O(i)Pr)4.
Catalytic Diastereo- and Enantioselective Synthesis of 2-Imidazolinones.
2019
Chiral cyclic ureas (2-imidazolinones) were prepared by the reaction of nitrones and isocyanoacetate esters using a multicatalytic system that combines a bifunctional Brønsted base-squaramide organocatalyst and Ag+ as a Lewis acid. The reaction could be achieved with a range of nitrones derived from aryl- and cycloalkylaldehydes with moderate diastereo- and good enantioselectivity. A plausible mechanism involving an initial formal [3 + 3] cycloaddition of the nitrone and isocyanoacetate ester, followed by rearrangement to an aminoisocyanate and cyclization to the imidazolinone, is proposed.
Model studies on a diastereoselective synthesis of the C(33)–C(37) fragment of Amphotericin B
2003
Abstract A new, short and highly diastereoselective synthetic route aiming at the C(33)–C(37) fragment of Amphotericin B has been developed. Studies with a model aldehyde (benzaldehyde) have given very promising results: the desired stereochemistry of all four stereocenters of the target molecule has been achieved with high diastereoselection. The stereochemistry of three key intermediates and the target segment has been confirmed by X-ray crystallography.
ChemInform Abstract: Enantioselective Synthesis of α-Quaternary Amino Acids by Alkylation of Deprotonated α-Aminonitriles.
2015
An α-alkylation of deprotonated α-amino nitriles, prepared from chiral phenyldioxanamine (I) by Strecker reaction, leads to α-quaternary arylglycines with high optical purity after hydrolysis and oxidative cleavage of the chiral auxiliary.
ChemInform Abstract: Enantioselective Addition of Nitromethane to α-Keto Esters Catalyzed by Copper(II)-Iminopyridine Complexes.
2008
The copper complex of a chiral iminopyridine easily prepared from (R)-(−)-fenchone and picolylamine catalyzes the enantioselective Henry (nitroaldol) reaction between nitromethane and α-keto esters. Good yields and modest to good enantioselectivities are obtained for a wide range of α-keto esters, bearing aromatic, alkyl or alkenyl groups attached to the ketone carbonyl group.
(S)-Mandelic acid enolate as a chiral benzoyl anion equivalent for the enantioselective synthesis of non-symmetrically substituted benzoins
2011
A strategy for the enantioselective synthesis of non-symmetrically substituted benzoins from (S)-mandelic acid and aromatic aldehydes has been developed. This strategy is based on a diastereoselective aldol reaction of the lithium enolate of the 1,3-dioxolan-4-one derived from (S)-mandelic acid and pivalaldehyde with aromatic aldehydes, which gives the corresponding aldols in good yields. Subsequent hydroxyl group protection as MEM ethers, basic hydrolysis of the dioxolanone ring, oxidative decarboxylation of the α-hydroxy acid moiety, and hydroxyl group deprotection provides chiral non-symmetrically substituted benzoins with high enantiomeric excesses.
Conjugate Alkynylation of Electrophilic Double Bonds. From Regioselectivity to Enantioselectivity
2018
This review surveys the historical efforts addressed toward the development of the conjugate alkynylation reaction. The regio- and enantioselective conjugate alkynylation of electron-deficient double bonds, most commonly unsaturated carbonyl compounds, has been an elusive reaction for a long time. Intensive research during the last decades has resulted in the identification of a number of effective reagents and catalysts to perform this reaction. Non-stereoselective conjugate alkynylation of unsaturated carbonyl compounds was first achieved by using preformed alkynyl organometallics and later with terminal alkynes under catalytic conditions. These methods paved the way for the development o…
ChemInform Abstract: Synthesis of Functionalized Indoles with an α-Stereogenic Ketone Moiety Through an Enantioselective Friedel-Crafts Alkylation wi…
2010
Chiral complexes of BINOL-based ligands with hafnium tert-butoxide catalyze the enantioselective Friedel-Crafts alkylation of indoles with (E)-1,4-diaryl-2-butene-1,4-diones at room temperature, with good yields and ee up to 94%. Hafnium(IV) was found to be a more effective Lewis acid than other frequently used metal ions such as titanium(IV) or zirconium(IV). Unlike the enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated compounds where the stereogenic center is generated in the β-position to a carbonyl group, the Friedel-Crafts alkylation with 2-butene-1,4-diones described here generates an α-stereogenic center with respect to one of the carbonyl groups. This can be…
Part II. Chiral dirhodium (II) catalysts with ortho-metalated arylphosphane ligands in the enantioselective intramolecular cyclopropanation of a race…
2006
Abstract In this report, chiral dirhodium (II) with ortho -metalated phosphane ligands, namely ( M )-Rh 2 (O 2 CR) 2 (PC) 2 [PC = ortho -metalated aryl phosphane, O 2 CR = carboxylate bridging ligands) ( 1a–g ), have been used for the intramolecular cyclopropanation of racemic1-diazo-6-methyl-3-(2-propenyl)-5-hepten-2-one ( 2 ), containing both a tri- and monosubstituted carbon–carbon double bond, in pentane. The highest level of regiocontrol has been obtained with chiral catalyst Rh 2 (O 2 CCH 3 ) 2 [( p -MeC 6 H 3 )P( p -MeC 6 H 4 ) 2 ] 2 ( M )- 1c , affording favorably trisubstituted cyclopropane 3 versus monosubstituted cyclopropane 4 in 74:26 ratio. An exceptional diastereoselectivity…
A Highly Regio-, Diastereo- and Enantioselective Intramolecular Cyclopropanation Reaction of a Racemic α-Diazo Ketone Catalyzed by Chiral ortho-Metal…
2003
Abstract A series of racemic dirhodium(II) compounds with two ortho-metalated aryl phosphine ligands in a head-to-tail arrangement Rh2(O2CR)2(pc)2 (pc=ortho-metalated aryl phosphine) (1a–k) were tested in the regio- and stereoselective cyclopropanation of racemic 1-diazo-6-methyl-3-(2-propenyl)-5-hepten-2-one 2, which possesses two different reactive CC double bonds for a five-membered-ring formation. The complexes Rh2(O2CCH3)2(pc)2 {pc=[(C6H4)P(C6H5)2], [(p-CH3C6H3)P(p-CH3C6H4)2], and [(C6H4)P(C6H5)(C6F5)]} (1a–d) successfully enhanced the cyclopropanation of trisubstituted versus monosubstituted CC bonds to give an 80:20 selectivity ratio. The reaction occurred with excellent diastereos…