Morita Baylis Hillman Adducts Research Articles

Synthesis and activity of novel homodimers of Morita–Baylis–Hillman adducts against Leishmania donovani: A twin drug approach

It is reported here the synthesis of novel Homodimers 12–19 of Morita–Baylis–Hillman adducts (MBHA) from one-pot Morita–Baylis–Hillman Reaction (MBHR) between aromatic aldehydes as eletrophiles and ethylene glycol diacrylate as Michael acceptor (35–94% yields) using cheap and green conditions. The bioactivities were evaluated against promastigote form of Leishmania donovani. All homodimers showed to be more potent than corresponding monomers. It is worth highlighting that the halogenated homodimers 17 and 18 (0.50μM) is almost 400 times more active than the corresponding monomer 10 and 1.24 times more potent than the second-line drug amphotericin B (0.62μM). Moreover, the selectivity index to 18 is very high (SIrb>400) far better than amphotericin B (SIrb=18.73). This is the first report of twin drugs strategy applied on Morita–Baylis–Hillman adducts.

ChemInform Abstract: Enantioselective Allylic Substitution of Morita—Baylis—Hillman Adducts Catalyzed by Chiral Bifunctional Ferrocenylphosphines.

AbstractAir‐stable chiral ferrocenylphosphines are synthesized and utilized in the asymmetric allylic substitution of Morita—Baylis—Hillman adducts with phthalimide under mild reaction conditions.

ChemInform Abstract: Synthesis of Poly‐Substituted Benzene from Morita—Baylis—Hillman Adducts via [3 + 1 + 2] Annulation Strategy: Palladium‐Catalyzed Domino Cyclization (5‐exo/3‐exo), Ring‐Expansion by Palladium Rearrangement, and Aromatization.

ChemInform Abstract: Synthesis of Poly‐Substituted Benzene from Morita—Baylis—Hillman Adducts via [3 + 1 + 2] Annulation Strategy: Palladium‐Catalyzed Domino Cyclization (5‐exo/3‐exo), Ring‐Expansion by Palladium Rearrangement, and Aromatization.

ChemInform Abstract: Synthesis of Hydrazinoheterocycles from Morita—Baylis—Hillman Adducts of Nitroalkenes with Azodicarboxylates.

AbstractA [3 + 2] annulation of hydrazinonitroalkenes, formed under Morita—Baylis—Hillman conditions, with naphthols involving Michael addition and cyclization as the key steps leads to arenodihydrofurans bearing a hydrazinodicarboxylate moiety.

Rhodium‐Catalyzed [2+2+2] Cycloadditions of Diynes with Morita–Baylis–Hillman Adducts: A Stereoselective Entry to Densely Functionalized Cyclohexadiene Scaffolds

AbstractA rhodium‐catalyzed asymmetric synthesis of 5,5‐disubstituted cyclohexa‐1,3‐dienes has been achieved by [2+2+2] cycloaddition reactions between diynes and Morita–Baylis–Hillman (M‐B‐H) adducts as unsaturated substrates. Products containing two adjacent chiral centres (quaternary and tertiary, respectively) were obtained with complete diastereoselectivity and high enantioselectivity (84–97%) through a kinetic resolution of the M‐B‐H adduct. Furthermore, these highly substituted cyclohexadienes reacted with dienophiles to afford the corresponding Diels–Alder cycloadducts in good yields.magnified image

An Efficient Synthesis of Dihydrobenzo[c]azepines from Morita–Baylis–Hillman Adducts via Pictet–Spengler Reaction

Various dihydrobenzo[c]azepines were synthesized in good yields via Pictet–Spengler cyclization protocol from tosylamide derivatives of Morita–Baylis–Hillman adducts and 1,3,5‐trioxane. The synthesis was carried out in the presence of easily removable montmorillonite K‐10 in short time in high yields.

ChemInform Abstract: Synthesis of 1,3,4‐Trisubstituted Benzenes from Morita—Baylis—Hillman Adducts of α‐Bromocinnamaldehyde via [5 + 1] Annulation Strategy.

ChemInform Abstract: Synthesis of 1,3,4‐Trisubstituted Benzenes from Morita—Baylis—Hillman Adducts of α‐Bromocinnamaldehyde via [5 + 1] Annulation Strategy.

Enantioselective Allylic Substitution of Morita–Baylis–Hillman Adducts Catalyzed by Chiral Bifunctional Ferrocenylphosphines

AbstractA series of air‐stable chiral ferrocenylphosphines (LB1–LB4) were prepared and used in the asymmetric allylic substitution of Morita–Baylis–Hillman (MBH) adducts with phthalimide under mild reaction conditions; the (R,SFc)‐ferrocenylphosphine LB4 afforded the desired amination products 3 in moderate yields with excellent enantioselectivities. The absolute configuration of 3o was confirmed by X‐ray analysis.

An Efficient Synthesis of α‐Isothiocyanato‐α,β‐unsaturated Esters from Morita–Baylis–Hillman Adducts

An Efficient Synthesis of α‐Isothiocyanato‐α,β‐unsaturated Esters from Morita–Baylis–Hillman Adducts

Regioselective addition–elimination of Morita–Baylis–Hillman adducts with 2-naphthol or phenol catalyzed by functionalized ionic liquids: a direct strategy to construct functional alkenes

A highly regioselective addition–elimination of Morita–Baylis–Hillman adducts promoted by base ionic liquids (0.5 mol%) was reported to afford a variety of functional alkenes in excellent yields (up to 99%). This protocol provides a new method to access functional alkenes directly. Recycled base ionic liquids could be reused at least five times and the isolated yield of the product was almost consistent after five runs.

ChemInform Abstract: [4 + 3] Cycloadditions with Bromo‐Substituted Morita—Baylis—Hillman Adducts of Isatins and N‐(ortho‐Chloromethyl)aryl Amides

Abstractto give challenging aza‐spirocycloheptane oxindole scaffolds

Synthesis of Poly‐Substituted Benzene from Morita–Baylis–Hillman Adducts Via [3 + 1 + 2] Annulation Strategy: Palladium‐catalyzed Domino Cyclization (5‐exo/3‐exo), Ring‐Expansion by Palladium Rearrangement, and Aromatization

Synthesis of Poly‐Substituted Benzene from Morita–Baylis–Hillman Adducts Via [3 + 1 + 2] Annulation Strategy: Palladium‐catalyzed Domino Cyclization (5‐<i>exo</i>/3‐<i>exo</i>), Ring‐Expansion by Palladium Rearrangement, and Aromatization

Synthesis of α-methylene-δ-oxo-γ-amino esters via Rh(ii)-catalyzed coupling of 1-sulfonyl-1,2,3-triazoles with Morita-Baylis-Hillman adducts.

A rhodium(ii)-catalyzed coupling of 1-sulfonyl-1,2,3-triazoles, prepared from 1-alkynes and sulfonyl azides, with Morita-Baylis-Hillman (MBH) adducts afforded highly functionalized α-methylene-δ-oxo-γ-amino esters in excellent yields with broad functional group tolerance. This transformation can also be successfully accomplished as a multicomponent all-in-one-pot reaction of 1-alkynes, sulfonyl azides and MBH adducts in the presence of Cu(i) and Rh(ii) catalysts.

Synthesis of hydrazinoheterocycles from Morita-Baylis-Hillman adducts of nitroalkenes with azodicarboxylates.

Conjugated nitroalkenes and nitrodienes undergo smooth α-hydrazination with azodicarboxylates through an imidazole catalyzed carbon-heteroatom bond formation under Morita-Baylis-Hillman conditions. The resulting hydrazinonitroalkenes take part in 1,3-dipolar cycloaddition with azide under mild conditions to give hydrazinotriazoles. A [3 + 2] annulation with phenols and naphthols involving Michael addition and cyclization as the key steps lead to arenodihydrofurans bearing a key hydrazinodicarboxylate moiety. Both regioisomers of naphthodihydrofurans could be synthesized by our methodology by employing the appropriate naphthol.

ChemInform Abstract: Morita—Baylis—Hillman Adducts as Building Blocks of Heterocycles: A Simple Approach to 4‐Substituted Pyrazolones, and Mechanism Investigation via ESI—MS(/MS).

AbstractEfficient approaches for the synthesis of 4‐substituted dihydropyrazolones starting from readily available Morita—Baylis—Hillman adducts (III) are developed.

Synthesis of 1,3,4‐Trisubstituted Benzenes from Morita–Baylis–Hillman Adducts of α‐Bromocinnamaldehyde via [5+1] Annulation Strategy

Synthesis of 1,3,4‐Trisubstituted Benzenes from Morita–Baylis–Hillman Adducts of α‐Bromocinnamaldehyde via [5+1] Annulation Strategy

Sequential Morita–Baylis–Hillman/Achmatowicz reactions: an expeditious access to pyran-3(6H)-ones with a unique substitution pattern

We herein disclosed a novel approach to synthesize densely functionalized 6-hydroxy-2H-pyran-3(6H)-ones with moderate to good diastereoselectivity. The method is based on a two step sequence using Morita–Baylis–Hillman adducts as substrates for the Achmatowicz rearrangement, allowing the preparation of highly substituted pyran-3-ones with overall yields ranging from 17% to 80% and a unique substitution pattern.

ChemInform Abstract: Morita—Baylis—Hillman Adduct Derivatives (MBHADs): Versatile Reactivity in Lewis Base‐Promoted Annulation

AbstractReview: [50 refs.

4 + 3] Cycloadditions with Bromo-Substituted Morita-Baylis-Hillman Adducts of Isatins and N-(ortho-Chloromethyl)aryl Amides.

Efficient construction of a challenging aza-spirocycloheptane oxindole scaffold is reported through an unprecedented [4 + 3] cycloaddition reaction with bromo-substituted Morita-Baylis-Hillman adducts of isatins and N-(ortho-chloromethyl)aryl amides. Both reactive intermediates, the allylic phosphonium ylides and aza-o-quinone methides, were in situ generated, chemoselectively facilitated by a Lewis base and Brønsted base, respectively.

Bipyridine carbaldehydes as electrophiles in the Morita–Baylis–Hillman reaction: synthesis of highly functionalized bipyridyl ligands and a macrocycle

A simple and efficient Morita–Baylis–Hillman (MBH) reaction of bipyridine carbaldehydes and unexplored activated alkenes afforded highly functionalized bipyridyl ligands. Particularly, one-pot MBH reaction of 2,2′-bipyridine-4,4′-dicarbaldehyde and 2,2′-bipyridine-4-methyl-4′-carbaldehyde with 1,6-hexanediol diacrylate afforded a twenty membered bipyridyl macrocycle and bis MBH adducts, respectively. Synthetic transformations of mono and bis MBH adducts thus obtained have been demonstrated by preparing bipyridyl N-oxide and [3+2]-cycloadduct of azomethine ylide derived from isatin and proline.