Stereoselective synthesis of N-heterocycles through amine addition to nitroalkenes

Gautam, Lekh Nath S.; Wang, Qiaoyi; Akhmedov, Novruz G.; Petersen, Jeffrey L.; Shi, Xiaodong

doi:10.1039/c3ob27452g

Cited by 14 publications

(4 citation statements)

References 32 publications

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“…Very interesting strategy for the synthesis of fluorinated nitrogen‐bearing heterocycles was proposed [105] . It based on the use of amines bearing pendant conjugated ester in the aza‐Michael addition.…”

Section: Aza‐michael Reactions With Other Pull‐pull Alkenesmentioning

confidence: 99%

“…Very interesting strategy for the synthesis of fluorinated nitrogen-bearing heterocycles was proposed. [105] It based on the use of amines bearing pendant conjugated ester in the aza-Michael addition. For example, upon treatment of β-CF 3 -nitroalkene 115 a with amine generated in situ from its hydrochloride 118 in the presence of Hunig's base (DIPEA) in acetonitrile at room temperature, the cyclization product 119 was obtained in high yield (Scheme 46).…”

Section: Aza-michael Reactions With Other Pull-pull Alkenesmentioning

confidence: 99%

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Pull‐Pull Alkenes in the Aza‐Michael Reaction

Rulev

Tyumentsev

2022

Adv Synth Catal

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Aza‐Michael addition is known to be one of the most exploited reactions in organic chemistry. Taking into account the fact that each seventh reaction in pharmaceutical industry involves the formation of at least one C−N bond, it is not surprising that this reaction is especially valuable for the synthesis of bioactive compounds and drugs. Traditionally, only push‐pull alkenes are regarded as starting material for this reaction. The participation of pull‐pull alkenes as Michael acceptors is much less studied. The presence of two vicinal electron‐withdrawing groups makes them highly reactive in nucleophilic reactions especially with nitrogen‐centered nucleophiles. This feature allows them to be excellent building blocks in the synthesis of bioactive molecules and polyfunctional materials. The review considers the most important and sometimes unexpected results obtained over the last two decades on the conjugate addition of nitrogen nucleophiles to pull‐pull alkenes bearing various acceptor moieties (alkoxycarbonyl‐, carbonyl‐, formyl‐, cyano‐, trifluoromethyl‐ or nitro group) in various combinations.

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Section: Aza‐michael Reactions With Other Pull‐pull Alkenesmentioning

confidence: 99%

Section: Aza-michael Reactions With Other Pull-pull Alkenesmentioning

confidence: 99%

Pull‐Pull Alkenes in the Aza‐Michael Reaction

Rulev

Tyumentsev

2022

Adv Synth Catal

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“…Asymmetric multicomponent reactions (AMCRs) are known to possess features that are well-suited for the construction of diverse chiral heterocyclic scaffolds from readily available starting materials, as can be seen from recent developments in the field of organocatalysis. ,− Therefore, organocatalytic AMCRs have emerged as a powerful tool in organic synthesis as they are facile, efficient, and have a high degree of atom economy. ,,,,,− The Biginelli reaction is a prominent example of an AMCR [aldehydes, β-ketoesters, and (thio)ureas] that has been extensively reviewed. ,, In 2006, Gong and co-workers demonstrated the first organocatalytic Biginelli reaction using H 8 -BINOL-based phosphoric acid 70 , on a wide variety of linear β-ketoesters, aldehydes, and (thio)ureas to yield the pharmaceutically important chiral dihydropyrimidinones (DHPMs) adducts with up to 97% ee (Scheme ). Application of this method to the synthesis of monastrol (a mitotic kinesin inhibitor) was also demonstrated with high optical purity (91% ee), using meta -TBSO-benzaldehyde with thiourea and ethyl acetoacetate.…”

Section: Noncovalent Catalysismentioning

confidence: 99%

Enantioselective Organocatalyzed Transformations of β-Ketoesters

et al. 2016

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The β-ketoester structural motif continues to intrigue chemists with its electrophilic and nucleophilic sites. Proven to be a valuable tool within organic synthesis, natural product, and medicinal chemistry, reports on chiral β-ketoester molecular skeletons display a steady increase. With the reignition of organocatalysis in the past decade, asymmetric methods available for the synthesis of this structural unit has significantly expanded, making it one of the most exploited substrates for organocatalytic transformations. This review provides comprehensive information on the plethora of organocatalysts used in stereoselective organocatalyzed construction of β-ketoester-containing compounds.

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“…The same strategy was applied by Shi et al for preparation of substituted pyrrolidines 24 through the reaction of amine 23 and nitroalkenes 15 with high yields and excellent diastereoselectivities (up to >99 : 1 dr) using Hünig's base (DIPEA) (Scheme 8). 24 The reaction proceeded via aza-Michael/Michael reaction cascade. By using a cyclic amine 25, the 5-5, 5-6, 6-5 or 6-6 bicyclic structures 26 can readily be prepared in good to excellent yields.…”

Section: Synthesis Of Five-membered Heterocyclesmentioning

confidence: 99%

Part I: Nitroalkenes in the synthesis of heterocyclic compounds

2014

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The applications of nitroalkenes in the synthesis of three-to five-membered O, N and S-heterocycles, including natural products are investigated in this review. These heterocyclic compounds were synthesized from nitroalkenes with a variety of substituents at the a and b-positions and those that were part of common and medium rings via a wide variety of reactions such as Michael addition reactions, epoxidation, [3 + 2] cycloaddition and many cascade/domino/tandem reactions. In addition, the potential of nitroalkenes to take part in multi-component and cascade reactions, particularly, in diastereo-and enantioselective versions is reviewed. The high reactivity of nitroalkenes and their potential to coordinate with the metal catalysts as well as organocatalysts signify them as efficient precursors in synthetic organic chemistry. Also, the flexibility of the nitro group in functional group manipulations has expanded the scope of the nitro group, in general, and nitroalkenes, in particular, in organic synthesis.

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Stereoselective synthesis of N-heterocycles through amine addition to nitroalkenes

Abstract: An efficient route for the preparation of substituted N-heterocycles was developed through the amine addition to nitroalkenes. The reaction tolerates a large substrate scope with good to excellent yields (up to 95%) and excellent stereoselectivities (up to 99 : 1 dr).

Cited by 14 publications

References 32 publications

Pull‐Pull Alkenes in the Aza‐Michael Reaction

Pull‐Pull Alkenes in the Aza‐Michael Reaction

Enantioselective Organocatalyzed Transformations of β-Ketoesters

Part I: Nitroalkenes in the synthesis of heterocyclic compounds

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