RESUMO
A Brønsted acid-catalyzed asymmetric Mannich-type addition of 1,3-diones to cyclic N-acyl ketimines is reported for the synthesis of enantioenriched isoindolinones. Various dicarbonyl-substituted isoindolinones bearing a quaternary carbon stereocenter were synthesized with excellent yields (up to 98%) and moderate to high enantioselectivities (up to 95% ee), and most of them possess a fluorine atom at the reactive center. Furthermore, the synthetic utility of the protocol has been demonstrated by the debenzoylation of the product.
RESUMO
Quinine derived bifunctional urea catalyzed cascade Michael-acyl transfer reaction of 5-alkenyl thiazolones and monofluorinated ß-diketones has been developed. The fluorine containing 4-acyloxy thiazoles were synthesized in high yields and good diastereo-and excellent enantioselectivities. Synthetic transformations, including synthesis of 4-hydroxy thiazoles, have been demonstrated.
RESUMO
An (R)-DM-BINAP/Cu(CH3CN)4BF4 complex catalyzed exo-selective asymmetric 1,3-dipolar cycloaddition (1,3-DCA) reaction of imino esters with α,ß-unsaturated pyrazoleamides has been developed. A series of highly functionalized pyrrolidines with multiple stereogenic centers were obtained with good yields and diastereoselectivities and excellent enantioselectivities (up to 99% ee).
RESUMO
Chiral Brønsted acid catalyzed enantioselective syntheses of isoindolinones and phthalides have been accomplished via tandem Mannich-lactamization and aldol-lactonization reactions, respectively. A variety of enantioenriched isoindolinones (up to 99% ee) and phthalides (up to 85% ee) containing α-diazoesters were afforded in excellent yields. Furthermore, a concise synthesis of ( S)-PD 172938 has been demonstrated by using this protocol.
RESUMO
A chiral phosphoric acid-catalyzed asymmetric Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines, derived from 3-hydroxyisoindolinones has been demonstrated in this communication. A variety of isoindolinone-based α-amino diazo esters bearing a quaternary stereogenic center were afforded in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the products has been depicted by the hydrogenation of the diazo moiety of adducts.
RESUMO
An efficient diastereo- and enantioselective route to access a wide range of highly substituted pyrrolidine and pyrrolizidine derivatives has been described via (1,3)- and double (1,3)-dipolar cycloaddition reactions catalyzed by the (R)-DM-SEGPHOS-Ag(I) complex. The reactions proceed smoothly at ambient temperature, affording a variety of pyrrolidines and pyrrolizidines in high yields (up to 93%) with up to 99:1 dr and excellent enantioselectivities (up to 98% ee) without any additives. The newly synthesized pyrrolidine and pyrrolizidine derivatives contain four and seven contiguous stereogenic centers, respectively. Moreover, the synthetic utility of enantioenriched products has been demonstrated by transforming them into various synthetically useful advanced intermediates.
RESUMO
Catalytic enantioselective direct vinylogous Michael addition of α,α-dicyanoalkenes to 2-enoylpyridine N-oxides with a bifunctional organocatalyst is described. The methodology offers an efficient way to install an asymmetric carbon-carbon bond at the γ-position of α,α-dicyanoalkenes in excellent regio-, diastereo-, and enantioselectivity. Further, application in desymmetrization of achiral α,α-dicyanoalkene to access highly functionalized enantioenriched cyclohexylidenemalononitrile derivatives has been demonstrated.
Assuntos
Nitrilas/química , Piridinas/química , Tioureia/química , Catálise , Estrutura Molecular , EstereoisomerismoRESUMO
A chiral PYBOX-DIPH-Zn(II) catalyzed enantioselective Mukaiyama-Michael reaction of acyclic silyl enol ethers with 2-enoylpyridine N-oxides has been studied in external additive free conditions at ambient temperature. The methodology offers straightforward access to a variety of functionalized chiral 1,5-dicarbonyl compounds, which could easily be elaborated into synthetically viable pyrones via hydrolysis followed by cyclization. A transition state model has been proposed to explain the stereochemical outcome.
RESUMO
An enantioselective Michael addition of cyclic 1,3-dicarbonyls to 2-enoylpyridine N-oxides catalyzed by a chiral pybox-diph-Zn(II) complex has been developed. The corresponding Michael adducts have been obtained in high yields with up to >99% ee. The Michael adduct has been transformed to biologically active 2,4-disubstituted hexahydroquinoline. A plausible transition-state model has been proposed to explain the stereochemical outcome of the reaction.
RESUMO
A potential pharmacologically active chiral 3-substituted 4-hydroxy-2-oxo-2H-chromene skeleton has been synthesized by enantioselective Michael addition catalyzed by PYBOX-DIPH-Zn(OTf)(2) complex. The methodology has successfully been employed in the synthesis of (R)-Warfarin and another related compounds.
Assuntos
Benzopiranos/química , Cumarínicos/síntese química , Ácidos de Lewis/química , Oxazóis/química , Compostos de Zinco/química , Benzopiranos/síntese química , Catálise , Cumarínicos/química , Estrutura Molecular , EstereoisomerismoRESUMO
An enantioselective Michael addition of malonates to 2-enoylpyridine N-oxides catalyzed by a chiral bisoxazoline-Zn(II) complex has been developed. The corresponding Michael adducts have been obtained in high yields with up to 96% ee. A plausible transition-state model has been proposed to explain the stereochemical outcome of the reaction.