Conjugate addition of 1,3-dicarbonyl compounds to maleimides using bifunctional primary amine‒(thio)phosphoramide organocatalysts

Efficient synthetic method for medicinally and opto-electronically important bichalcophenes is reported, which highlights Mn(OAc)3/CoCl2-catalyzed oxidative deacetylation of 1,5-dicarbonyl compounds that were easily prepared by conjugate addition of ethyl acetoacetate to α,β-unsaturated carbonyl compounds containing a chalcophene unit. Paal–Knorr reaction of the resulting 1,4-dicarbonyl compounds produced 4-phenyl-2,2′-bichalcophenes and their aza-analogues.

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The role of reversibility in the enantioselective conjugate addition of α,α-disubstituted aldehydes to nitro-olefins catalyzed by primary amine thioureas

Catalysis Science & Technology ◽

10.1039/c4cy00648h ◽

2014 ◽

Vol 4 (10) ◽

pp. 3505-3509 ◽

Cited By ~ 5

Author(s):

Yining Ji ◽

Donna G. Blackmond

Keyword(s):

Primary Amine ◽

Conjugate Addition ◽

Mechanistic Insight

Identification of intermediates in the asymmetric conjugate addition of aldehdyes to nitro-olefins catalyzed by primary amine thioureas add mechanistic insight.

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Organocatalytic Asymmetric Conjugate Addition of Aldehydes to Maleimides and Nitroalkenes in Deep Eutectic Solvents

Molecules ◽

10.3390/molecules24224058 ◽

2019 ◽

Vol 24 (22) ◽

pp. 4058 ◽

Cited By ~ 3

Author(s):

Alejandro Torregrosa-Chinillach ◽

Alba Sánchez-Laó ◽

Elisa Santagostino ◽

Rafael Chinchilla

Keyword(s):

Primary Amine ◽

Room Temperature ◽

Deep Eutectic Solvents ◽

Conjugate Addition ◽

Reaction Media

A chiral primary amine-salicylamide is used as an organocatalyst for the enantioselective conjugate addition of α,α-disubstituted aldehydes to maleimides and nitroalkenes. The reactions are performed in deep eutectic solvents as reaction media at room temperature, leading to the corresponding adducts with enantioselectivities up to 88% (for maleimides) and 80% (for nitroalkenes). Catalyst and solvent can be recovered and reused.

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Asymmetric Conjugate Addition of α-Cyanoketones to Benzoyl Acrylonitrile Derivatives Using a Diaminomethylenemalononitrile Organocatalyst

Synthesis ◽

10.1055/s-0040-1707285 ◽

2020 ◽

Vol 52 (24) ◽

pp. 3874-3880 ◽

Cited By ~ 1

Author(s):

Tsuyoshi Miura ◽

Hiroshi Akutsu ◽

Kosuke Nakashima ◽

Yuta Kanetsuna ◽

Masahiro Kawada ◽

...

Keyword(s):

Catalytic Activity ◽

Conjugate Addition ◽

Significant Loss ◽

Addition Reactions ◽

Dicarbonyl Compounds ◽

Stereogenic Centers ◽

Synthetic Intermediates ◽

Quaternary Stereogenic Centers

AbstractA diaminomethylenemalononitrile (DMM) organocatalyst was used to efficiently promote asymmetric conjugate addition of various α-cyanoketones to benzoyl acrylonitrile derivatives. The corresponding 1,5-dicarbonyl compounds containing vicinal tertiary and quaternary stereogenic centers are versatile synthetic intermediates and were obtained in good yields and with excellent enantioselectivities (up to 96% ee). The present study describes the first successful examples of asymmetric conjugate addition reactions of α-cyanoketones with benzoyl acrylonitriles. In addition, the DMM organocatalyst can be recovered and reused up to five times without significant loss of either catalytic activity or enantioselectivity.

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