Organocatalytic and enantioselective Michael reaction between α-nitroesters and nitroalkenes. <i>Syn</i>/<i>anti-</i>selectivity control using catalysts with the same absolute backbone chirality

Martínez, José Ignacio Homobono; Uria, Uxue; Muñiz, Maria C.; Reyes, Efraím; Carrillo, Luisa; Vicario, José L.

doi:10.3762/bjoc.11.277

Cited by 5 publications

(2 citation statements)

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“…Carrillo, Vicario, and co‐workers demonstrated a catalyst‐controlled diastereodivergent Michael addition of α‐substituted α‐nitroacetates 23 and nitroalkenes 24 for the synthesis of 2,4‐dinitro esters 25 , employing tert ‐amine‐squaramide bifunctional catalysts (Scheme ). The anti ‐ and syn ‐diastereomers of the Michael adducts were achieved with good to excellent enantio‐ and diastereoselectivities by a cyclohexanediamine‐derived squaramide catalyst 26 and a Cinchona ‐derived squaramide catalyst 27 , respectively.…”

Section: Organocatalytic Diastereodivergent Reactionsmentioning

confidence: 99%

Advances in Asymmetric Diastereodivergent Catalysis

2017

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Because the biological and/or pharmacologicalp roperties of ag iven molecule often depend on the absolutea nd relative configurations of the stereogenic centers,d ifferent diastereomers may exhibit totally different biological and/or pharmacological activities.T herefore,f or compoundsc ontaining multiple stereogenic centers,t he stereoselective asymmetric synthesis of all of the individual diastereomers, preferably using ac atalytic method, is of great interest andi mportance in organic synthesis and drug discovery.I nt his context, the development of catalytic diastereodivergent methods is highly desirable,s incei tp rovides one of the most efficient ways to access multipled iastereomers from the same substrates.T he current review attemptst os umma-rize the developments in the field of asymmetric diastereodivergent catalysis. Scheme 5. Michaelr eactions for the synthesis of both syn-and anti-diastereomers. Scheme 6. Diastereodivergent tandem Michael-Michael reaction. Scheme 8. Diastereodivergent aldol reactionsofc ycloketones andaryl aldehydes. Scheme 9. l-Proline/guanidinium salt co-catalyzed diastereodivergent aldol reactions. Scheme 7. Diastereodivergent synthesis of 2,4-dinitro ester derivatives using bifunctional squaramidec atalysts. Scheme 11. Diastereodivergent synthesis of spirooxindole derivatives.Scheme 12. Diastereodivergent synthesis of bis(spirocyclic)oxindoles derivatives. Scheme 14. Diastereodivergent formal hydroaminination, hydrooxidation, and reductive Mannich reaction of enal 52. Scheme 15. Diastereodivergent alkylamination, diamination, and aminooxidation of enal 64. Scheme 16. Generation of diastereodivergence in the one-pot sequential cycle-specific catalysis. Scheme 17. Organocatalytic diastereodivergent synthesis of furan-fused carbocycles. Scheme 18. Accesstot he full matrixo fthe stereoisomers of the annulated furan. Scheme 19. Diastereodivergent cascade reaction towards chiral diamine derivatives. Scheme 23. Diastereodivergent synthesis of indolo[2,3-a]-, benzo[a]-, and thieno[3,2-a]quinolizidine skeletons. Scheme 24. Diastereodivergent [4+ +2] cycloaddition of cyclic enones with alkenyl-or alkynylmethylidenemalononitriles. Scheme 25. Diastereodivergent synthesis of cyclohexane derivativesu sing bifunctional squaramide catalysts. Scheme 26. Diastereodivergent synthesis of polyfuntionalized cyclohexanes using MDOs. Scheme 27. Enantioselectived iastereodivergentsynthesis of lycorane diastereomers using MDOs. Scheme 28. Diastereodivergent tandem hetero-Diels-Alder/oxa-Michael reaction catalyzed by MDOs. Scheme 29. Diastereodivergent approach towards dihydrobezofuran derivatives. Scheme 30. Diastereodivergent approach towards tetrahydrofuran derivatives. Scheme 31. Proposed transition states leading to cis-a nd trans-dihydrobenzofuran derivatives. Scheme 32. Adiastereodivergent[4 + +2] annulation of 16 and 127. Scheme 35. Diastereodivergent cycloaddition of azomethine ylides with C 60 . Scheme 36. Diastereodivergent synthesis of the four stereoisomers of the pyrrolidinoendofullerenes. S...

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Section: Organocatalytic Diastereodivergent Reactionsmentioning

confidence: 99%

Advances in Asymmetric Diastereodivergent Catalysis

2017

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“…While there have been considerable studies on the synthesis of α-amino acids, there are still few intermolecular catalytic asymmetric C–C bond-forming methods that are successful in forging the α-quaternary vic -diamine and diamino acid motifs with both high diastereoselection and enantioselection while providing useful isolated yields. ,, Approaches that address all three of these criteria enhance accessibility, and those that use similar catalysts to achieve reagent control over diastereoselection impart an ease of synthesis. The use of a single catalyst design to provide selective access to both anti - and syn -diastereomers while simultaneously controlling enantioselectiontermed diastereodivergent , is uncommon, but a growing number of transformations have been addressed by combinations of distinct catalysts. − More common are solutions involving the use of chiral nonracemic reagents to activate nucleophile and electrophile independently ( vide infra ), while single-reagent systems to achieve similar selectivity control are quite rare. − …”

Section: Introductionmentioning

confidence: 99%

DFT-Based Stereochemical Rationales for the Bifunctional Brønsted Acid/Base-Catalyzed Diastereodivergent and Enantioselective aza-Henry Reactions of α-Nitro Esters

et al. 2021

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A pair of chiral bis(amidine) [BAM] proton complexes provide reagent (catalyst)-controlled, highly diastereoand enantioselective direct aza-Henry reactions leading to α-alkylsubstituted α,β-diamino esters. A C 2 -symmetric ligand provides high anti-selectivity, while a nonsymmetric congener exhibits synselectivity in this example of diastereodivergent, enantioselective catalysis. A detailed computational analysis is reported for the first time, one that supports distinct models for selectivity resulting from the more hindered binding cavity of the C 1 -symmetric ligand. Binding in this congested pocket accommodates four hydrogen bond contacts among ligands and substrates, ultimately favoring a pre-syn arrangement highlighted by pyridinium-azomethine activation and quinolinium-nitronate activation. The complementary transition states reveal a wide range of alternatives. Comparing the C 1 -and C 2 -symmetric catalysts highlights distinct electrophile binding orientations despite their common hydrogen bond donor−acceptor features. Among the factors driving unusual high syndiastereoselection are favorable dispersion forces that leverage the anthracenyl substituent of the C 1 -symmetric ligand.

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